Rinse added fabric softening compositions and method of use for the delivery of fragrance derivatives

ABSTRACT

The present invention relates to a fragrance delivery system for use in laundry detergent compositions which provides a long lasting &#34;freshness&#34; or &#34;clean&#34; scent to fabric. The compositions described herein deliver highly fabric substantive pro-accords to the fabric surface during laundering wherein the pro-accords release their fragrance raw materials over a period of up to two weeks. The present invention also relates a method for delivering a pleasurable scent to fabric which has a lasting freshness quality by contacting the fabric with a laundry detergent composition which comprises the fragrance-releasable pro-accords.

This application claims the priority of U.S. Provisional Application60/024,117, filed Aug. 19, 1996.

FIELD OF THE INVENTION

The present invention relates to rinse added fabric softeningcompositions containing β-keto-ester pro-fragrance compounds and methodsfor accomplishing the delivery of such organic pro-fragrance compoundsto textile articles and other surfaces rinsed with said compositions.More particularly, the invention relates to rinse added fabric softeningcompositions in which there is a delayed release of fragrances fromsurfaces rinsed in an aqueous bath in the presence of conventionalfabric softening ingredients.

BACKGROUND OF THE INVENTION

Most consumers have come to expect scented laundry products and toexpect that fabrics which have been laundered to also have a pleasingfragrance. It is also desired by consumers for laundered fabrics tomaintain the pleasing fragrance over time. Perfume additives makelaundry compositions more aesthetically pleasing to the consumer, and insome cases the perfume imparts a pleasant fragrance to fabrics treatedtherewith. However, the amount of perfume carry-over from an aqueouslaundry bath onto fabrics is often marginal and does not last long onthe fabric. Fragrance materials are often very costly and theirinefficient use in rinse added fabric softener compositions andineffective delivery to fabrics from the rinse results in a very highcost to both consumers and fabric softener manufacturers. Industry,therefore, continues to seek with urgency for more efficient andeffective fragrance delivery in fabric softener products, especially forimprovement in the provision of long-lasting fragrance to the rinsedfabrics.

Carrier mechanisms for perfume delivery, such as by encapsulation, havebeen taught in the prior art. See for example, U.S. Pat. No. 5,188,753.

U.S. Pat. No. 5,378,468, Suffis et al, issued Jan. 3, 1995 describesspecific types of personal care compositions, such as deodorant sticks,comprising assertedly "body-activated" fragrances. The term apparentlyrefers to the previously known tendency of materials such as acetals andketals derived from fragrance alcohols to hydrolyze under acidic pHconditions thereby releasing fragrance. See, for example, U.S. Pat. No.3,932,520, Hoffman, issued Jan. 13, 1976.

See also, Steffen Arctander, "Perfume and Flavor Chemicals", Arctander,N.J., 1969. Factors affecting substantivity of fragrance materials onfabrics are discussed in Estcher et al. JAOCS 71 p. 31-40 (1994).

The selected potential fragrance materials described by Suffis et alinclude particular acetals and ketals, exemplified by propylene glycolvanillin acetal. The materials exemplified apparently are ratherhydrophilic short chain alcohol or diol derivatives of fragrancealdehydes and ketones that upon hydrolysis, deliver one mole of thealdehyde per mole of the potential fragrance material. The presentinventors believe that short chain hydrophilic acetal and ketalmaterials are incompatible with acidic rinse added fabric softeningcompositions as described hereinafter. The Suffis et al development isdesigned to be incorporated with a personal care product vehicle,resulting in clear deodorant sticks and the like.

For rinse added fabric softening use, it is important that ratherhydrophobic pro-fragrant compounds be used in order to enhancedeposition onto surfaces in the wash solution and retention on thewashed surface during rinsing. In Suffis et al, the compositionscontaining the potential fragrance materials are applied directly to thesubstrate (i.e. skin); therefore, the deposition problems resulting fromdilution, rinsing, etc. are not at issue.

Esters of perfume alcohols are known in the art for providing extendeddelivery of fragrances in fabric softening compositions. See, forexample, U.S. Pat. No. 5,531,910, Severns, issued Jul. 2, 1996. However,the manufacture of pro-fragrant esters known in the art can presentcostly and significant synthetic challenges. Derivitization of tertiaryfragrance alcohols into simple esters is particularly difficult, oftenresulting in low yields and increased levels of less desirable sideproducts. Therefore, industry continues to seek improved alternativesfor generating pro-fragrances through economic and effective means.

It has now surprisingly been discovered that these problems canunexpectedly be overcome by the use of β-keto-esters as pro-fragrances.The hydrophobic β-keto-esters of the present invention demonstrateimproved substantivity through the rinse. These ingredients furtherprovide sustained gradual release of fragrance raw materials, especiallyfragrance raw material alcohols and ketones, from laundry items over anextended period of time. The use of β-ketoesters also provides analternative synthetic route to derivatize fragrance raw materialalcohols into pro-fragrance compounds. This method is particularly wellsuited to derivatization of tertiary alcohols. Tertiary alcohols can bederivatized with higher yields and improved purity via this method.

BACKGROUND ART

The following relate to the subject matter of fragrance ingredients.U.S. Pat. No. 5,626,852 Suffis et al., issued May 6, 1997; U.S. Pat. No.5,232,612 Trinh et al., issued Aug. 3, 1996; U.S. Pat. No. 5,506,201McDermott et al., issued Apr. 9, 1996; U.S. Pat. No. 5,266,592 Grub etal., issued Nov. 30, 1993; U.S. Pat. No. 5,081,111 Akimoto et al.,issued Jan. 14, 1992; U.S. Pat. No. 4,994,266 Wells, issued Feb. 19,1991; U.S. Pat. No. 4,524,018 Yemoto et al., issued Jun. 18, 1985; U.S.Pat. No. 3,849,326 Jaggers et al., issued Nov. 19, 1974; U.S. Pat. No.3,779,932 Jaggers et al., issued Dec. 18, 1973; JP 07-179,328 publishedJul. 18, 1995; JP 05-230496 published Sep. 7, 1993; WO 96/14827published May 23, 1996; WO 95/04,809 published Feb. 16, 1995; and WO95/16660 published Jun. 22, 1995. In addition, P. M. Muller, D.Lamparsky Perfumes Art, Science, & Technology Blackie Academic &Professional, (New York, 1994) is included herein by reference.

SUMMARY OF THE INVENTION

The present invention meets the aforementioned needs in that it has beensurprisingly discovered that fragrance raw material alcohols can bedelivered onto fabric by way of rinse added fabric softeningcompositions from a single precursor pro-fragrance molecule having highfabric substantivity and that these pro-fragrances thereby impart a"fresh" or "clean" aesthetic residual odor benefit to the fabric. Inaddition to the short-term pleasurable odor benefits, the pro-fragrancesaccording to the present invention continue to release their fragranceraw materials for as long as several weeks depending upon the structureof the pro-fragrance.

The pro-fragrances described herein comprise fragrance raw materialalcohols in a stable, releasable β-ketoester form. The pro-fragrancecontaining rinse added fabric conditioning compositions of the presentinvention can comprise any number of pro-fragrances which when takentogether are capable of releasing complex perfume accords which comprisefragrance raw material alcohols, ketones, etc. In addition, thepro-fragrances of the present invention are suitable for delivery of anytype of fragrance "characteristic" desired by the formulator.

The first aspect of the present invention relates to rinse added fabricsoftening compositions which provide fabric with enhanced fragrancelongevity, comprising:

a) at least about 0.01%, preferably from about 0.01% to about 15%, morepreferably from about 0.1% to about 10%, most preferably from about 0.2%to about 1% by weight, of a β-ketoester having the formula: ##STR1##wherein R is C₁ -C₃₀ substituted or unsubstituted linear alkyl, C₃ -C₃₀substituted or unsubstituted branched alkyl, C₃ -C₃₀ substituted orunsubstituted cyclic alkyl, C₂ -C₃₀ substituted or unsubstituted linearalkenyl, C₃ -C₃₀ substituted or unsubstituted branched alkenyl, C₃ -C₃₀substituted or unsubstituted cyclic alkenyl, C₂ -C₃₀ substituted orunsubstituted linear alkynyl, C₃ -C₃₀ substituted or unsubstitutedbranched alkynyl, C₆ -C₃₀ substituted or unsubstituted alkylenearyl, C₆-C₃₀ substituted or unsubstituted aryl, and mixtures thereof; R¹ is analkoxy unit derived from a fragrance raw material alcohol; R² and R³ areeach independently selected from the group consisting of hydrogen, C₁-C₂₀ substituted or unsubstituted linear alkyl, C₃ -C₂₀ substituted orunsubstituted branched alkyl, C₂ -C₂₀ substituted or unsubstitutedalkyleneoxy, C₃ -C₂₀ substituted or unsubstituted alkyleneoxyalkyl, C₇-C₂₀ substituted or unsubstituted alkylenearyl, C₆ -C₂₀ substituted orunsubstituted alkyleneoxyaryl, and mixtures thereof; and

b) from about 85% to about 99.99% by weight, of ingredients useful forformulating fabric softening compositions.

The compositions of the present invention preferably comprise from about1% to about 80%, preferably from about 5 to about 50% of cationic fabricsoftening compound. Dilute liquid compositions of the present inventionpreferably contain from about 5% to about 15% of cationic fabricsoftening compound. Concentrated liquid compositions of the presentinvention preferably contain from about 15% to about 50%, morepreferably from about 15% to about 35% of cationic fabric softeningcompound. Preferably, the cationic fabric softening compound is selectedfrom biodegradable quaternary ammonium compounds as describedhereinafter.

The present invention also encompasses a method for contactingcompositions comprising said pro-fragrant β-keto-ester as describedhereinbefore with a fabric. Preferred is a method for laundering soiledfabrics, comprising contacting said fabrics with an aqueous mediumcontaining at least about 50 ppm, preferably from about 100 ppm to about10,000 ppm of a rinse added fabric softening composition according tothe above, preferably with agitation. Said method includes the processof treating textiles in a rinse cycle of a washing machine comprisingthe step of contacting textiles in a washing machine with a fabricsoftening effective amount of a rinse added fabric softening compositioncomprising:

(a) from about 0.01% to about 15%, by weight of a β-ketoesterpro-fragrance described herein; and

(b) from about 85% to about 99.99%, by weight of the composition, ofingredients useful for formulating fabric softening compositions.

The present invention also relates to novel β-ketoester pro-fragrancematerials which are suitable for use in delivering lasting fragrancebenefits to fabric. These and other objects, features and advantageswill become apparent to those of ordinary skill in the art from areading of the following detailed description and the appended claims.

All percentages, ratios and proportions herein are by weight, unlessotherwise specified. All temperatures are in degrees Celsius (° C.)unless otherwise specified. All documents cited are in relevant part,incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION

The rinse added fabric softening compositions of the present inventioncomprise one or more β-ketoester "pro-fragrance" compounds which aredeposited onto the fabric surface during the laundry wash cycle andwhich are capable of releasing a fragrance raw material alcohol. The keyadvantages provided by the β-ketoester pro-fragrances of the presentinvention include chemical stability in the final product matrix, easeof formulation into the product matrix, and a highly desirable rate offragrance raw material release. The product matrix is preferably liquid,however, granular, gelatenous, or viscous liquid embodiments are notexcluded as suitable embodiments.

The β-ketoester "pro-fragrances" of the present invention begindelivering the fragrance raw material alcohols to the fabric surface assoon as the rinse added fabric softening composition is added to thelaundry liquor. These "pro-fragrance" compounds are rapidly depositedonto the fabric surface due to the high fabric substantivity of thecompounds and once deposited, begin to release the fragrance rawmaterial alcohols during the remainder of the wash cycle and dryingcycles. Because the β-ketoester pro-fragrances of the present inventiongenerally have a higher molecular weight than uncombined fragrance rawmaterial alcohols and are therefore less volatile, the pro-fragrances ofthe present invention are a means for effectively delivering fragranceraw material alcohols to the fabric surface even upon exposure toprolonged heating which occurs during automatic dryer usage followingdeposition of the compounds upon fabric during the laundry rinse cycle.Once the laundry cycle is complete, that is the clothing or fabric isdry and ready for use, the "pro-fragrance" continues to release thefragrance raw materials and because this release of material isprotracted, the fabric remains smelling "fresh" and "clean" longer.

Most of the fragrance raw material alcohols and ketones which comprisethe β-ketoester pro-fragrances of the present invention are notsufficiently deliverable as individual compounds to fabric via the rinsecycle either due to solubility factors (not sufficiently soluble in thelaundry liquor), substantivity factors (do not sufficiently adhere tofabric surface), or volatility factors (evaporation during storage).Therefore, the pro-fragrances described herein are a means fordelivering certain fragrance raw materials to fabric which could nothave previously been effectively or efficiently delivered.

For the purposes of the present invention "fragrance raw materials" areherein defined as alcohols, ketones, esters, ethers, alkanes, andalkenes, especially mixed functionality compounds, for example,terpenes, having a molecular weight of at least about 100 g/mol andwhich are useful in imparting an odor, fragrance, essence, or scenteither alone or in combination with other "fragrance raw materials".

β-Ketoester Pro-fragrances

The compositions according to the present invention comprise one or moreβ-ketoesters having the formula: ##STR2## wherein R is C₁ -C₃₀substituted or unsubstituted linear alkyl, C₃ -C₃₀ substituted orunsubstituted branched alkyl, C₃ -C₃₀ substituted or unsubstitutedcyclic alkyl, C₂ -C₃₀ substituted or unsubstituted linear alkenyl, C₃-C₃₀ substituted or unsubstituted branched alkenyl, C₃ -C₃₀ substitutedor unsubstituted cyclic alkenyl, C₂ -C₃₀ substituted or unsubstitutedlinear alkynyl, C₃ -C₃₀ substituted or unsubstituted branched alkynyl,C₆ -C₃₀ substituted or unsubstituted alkylenearyl, C₆ -C₃₀ substitutedor unsubstituted aryl, and mixtures thereof; R² and R³ are eachindependently selected from the group consisting of hydrogen, C₁ -C₂₀substituted or unsubstituted linear alkyl, C₃ -C₂₀ substituted orunsubstituted branched alkyl, C₂ -C₂₀ substituted or unsubstitutedalkyleneoxy, C₃ -C₂₀ substituted or unsubstituted alkyleneoxyalkyl, C₇-C₂₀ substituted or unsubstituted alkylenearyl, C₆ -C₂₀ substituted orunsubstituted alkyleneoxyaryl, and mixtures thereof.

The β-ketoester pro-fragrances of the present invention are either"substituted" or "unsubstituted" β-ketoesters. For the purposes of thepresent invention the term "unsubstituted β-ketoester" is defined as "aβ-ketoester pro-fragrance wherein each R² and R³ is hydrogen" and"substituted β-ketoester" is defined as "a ,-ketoester pro-fragrancewherein at least one R² or R³ is not a hydrogen".

For the purposes of the present invention the term "substituted" as itapplies to linear alkyl, branched alkyl, cyclic alkyl, linear alkenyl,branched alkenyl, cyclic alkenyl, alkynyl, and branched alkynyl unitsare defined as "carbon chains which comprise substitutents other thanbranching of the carbon atom chain", for example, other than thebranching of alkyl units (e.g. isopropyl, isobutyl). Non-limitingexamples of "substituents" include hydroxy, C₁ -C₁₂ alkoxy, preferablymethoxy; C₁ -C₁₂ branched alkoxy, preferably isopropoxy; C₁ -C₁₂ cyclicalkoxy; nitrilo; halogen, preferably chloro and bromo, more preferablychloro; nitro; morpholino; cyano; carboxyl, non-limiting examples ofwhich are --CHO; --CO₂ H; --CO₂ ⁻ M⁺, --CO₂ R'; --CONH₂ ; --CONHR⁷ ;--CONR⁷ ₂ ; wherein R⁷ is C₁ -C₁₂ linear or branched alkyl); --SO₃ ⁻ M⁺; --OSO₃ ⁻ M⁺ ; --N(R⁸)₂ ; and --N⁺ (R⁸)₃ X⁻ wherein each R⁸ isindependently hydrogen or C₁ -C₄ alkyl; and mixtures thereof; wherein Mis hydrogen or a water soluble cation; and X is chlorine, bromine,iodine, or other water soluble anion.

For the purposes of the present invention substituted or unsubstitutedaryl units are defined as phenyl moieties having the formula: ##STR3##or α and β-naphthyl moieties having the formula: ##STR4## wherein R⁵ andR⁶ can be substituted on either ring, alone or in combination, and R⁵and R⁶ are each independently hydrogen, hydroxy, C₁ -C₆ alkyl, C₂ -C₆alkenyl, C₁ -C₄ alkoxy, C₁ -C₆ branched alkoxy, nitrilo, halogen, nitro,morpholino, cyano, carboxyl (--CHO; --CO₂ H; --CO₂ ⁻ M⁺, --CO₂ R⁷ ;--CONH₂ ; --CONHR⁷ ; --CONR⁷ ₂ ; wherein R⁷ is C₁ -C₁₂ linear orbranched alkyl), --SO₃ ⁻ M⁺, --OSO₃ ⁻ M⁺, --N(R⁸)₂, and --N⁺ (R⁸)₃ X⁻wherein each R⁸ is independently hydrogen or C₁ -C₄ alkyl; and mixturesthereof; and mixtures thereof. R⁵ and R⁶ are preferably hydrogen C₁ -C₆alkyl, --CO₂ ⁻ M⁺, --SO₃ ⁻ M⁺, --OSO₃ ⁻ M⁺, and mixtures thereof, morepreferably R⁵ or R⁶ is hydrogen and the other moiety is C₁ -C₆ ; whereinM is a water soluble cation and X is chlorine, bromine, iodine, or otherwater soluble anion. Examples of other water soluble anions includeorganic species such as fumarate, tartrate, oxalate and the like,inorganic species include sulfate, hydrogen sulfate, phosphate and thelike.

For the purposes of the present invention substituted or unsubstitutedalkylenearyl units are defined as alkylenephenyl moieties having theformula: ##STR5## or alkylenenaphthyl moieties having the formula:##STR6## wherein R⁵ and R⁶ can be substituted on either ring, alone orin combination, and R⁵ and R⁶ are each independently hydrogen, hydroxy,C₁ -C₆ alkyl, C₂ -C₆ alkenyl, C₁ -C₄ alkoxy, C₁ -C₆ branched alkoxy,nitrilo, halogen, nitro, morpholino, cyano, carboxyl (--CHO; --CO₂ H;--CO₂ ⁻ M⁺, --CO₂ R⁷ ; --CONH₂ ; --CONHR⁷ ; --CONR⁷ ₂ ; wherein R⁷ is C₁-C₁₂ linear or branched alkyl), --SO₃ ⁻ M⁺, --OSO₃ ⁻ M⁺, --N(R⁸)₂, and--N+(R⁸)₃ X⁻ wherein each R⁸ is independently hydrogen or C₁ -C₄ alkyl;and mixtures thereof; and mixtures thereof, p is from 1 to about 24. R⁵and R⁶ are preferably hydrogen C₁ -C₆ alkyl, --CO₂ ⁻ M⁺, --SO₃ ⁻ M⁺,--OSO₃ ⁻ M⁺, and mixtures thereof, more preferably R⁵ or R⁶ is hydrogenand the other moiety is C₁ -C₆ ; wherein M is a water soluble cation andX is chlorine, bromine, iodine, or other water soluble anion. Examplesof other water soluble anions include organic species such as fumarate,tartrate, oxalate and the like, inorganic species include sulfate,hydrogen sulfate, phosphate and the like.

For the purposes of the present invention substituted or unsubstitutedalkyleneoxy units are defined as moieties having the formula: ##STR7##wherein R⁵ is hydrogen; R⁶ is hydrogen, methyl, ethyl, and mixturesthereof; the index x is from 1 to about 10.

For the purposes of the present invention substituted or unsubstitutedalkyleneoxyalkyl are defined as moieties having the formula: ##STR8##wherein R⁵ is hydrogen, C₁ -C₁₈ alkyl, C₁ -C₄ alkoxy, and mixturesthereof; R⁶ is hydrogen, methyl, ethyl, and mixtures thereof; the indexx is from 1 to about 9 and the index y is from 2 to about 18.

For the purposes of the present invention substituted or unsubstitutedalkyleneoxyaryl units are defined as moieties having the formula:##STR9## wherein R⁵ and R⁶ can be substituted on either ring, alone orin combination, and R⁵ and R⁶ are each independently hydrogen, hydroxy,C₁ -C₆ alkyl, C₂ -C₆ alkenyl, C₁ -C₄ alkoxy, C₁ -C₆ branched alkoxy,nitrilo, halogen, nitro, morpholino, cyano, carboxyl (--CHO; --CO₂ H;--CO₂ ⁻ M⁺, --CO₂ R'; --CONH₂ ; --CONHR⁷ ; --CONR⁷ ₂ ; wherein R⁷ is C₁-C₁₂ linear or branched alkyl), --SO₃ ⁻ M⁺, --OSO₃ ⁻ M⁺, --N(R⁸)₂, and--N+(R⁸)₃ X⁻ wherein each R⁸ is independently hydrogen or C₁ -C₄ alkyl;and mixtures thereof; and mixtures thereof, p is from 1 to about 24. R⁵and R⁶ are preferably hydrogen C₁ -C₆ alkyl, --CO₂ ⁻ M⁺, -SO₃ ⁻ M⁺,--OSO₃ ⁻ M⁺, and mixtures thereof, more preferably R⁵ or R⁶ is hydrogenand the other moiety is C₁ -C₆ ; wherein M is a water soluble cation andX is chlorine, bromine, iodine, or other water soluble anion. Examplesof other water soluble anions include organic species such as fumarate,tartrate, oxalate and the like, inorganic species include sulfate,hydrogen sulfate, phosphate and the like.

R units are C₁ -C₃₀ substituted or unsubstituted linear alkyl, C₃ -C₃₀substituted or unsubstituted branched alkyl, C₃ -C₃₀ substituted orunsubstituted cyclic alkyl, C₂ -C₃₀ substituted or unsubstituted linearalkenyl, C₃ -C₃₀ substituted or unsubstituted branched alkenyl, C₃ -C₃₀substituted or unsubstituted cyclic alkenyl, C₂ -C₃₀ substituted orunsubstituted linear alkynyl, C₃ -C₃₀ substituted or unsubstitutedbranched alkynyl, C₆ -C₃₀ substituted or unsubstituted alkylenearyl, C₆-C₃₀ substituted or unsubstituted aryl, and mixtures thereof. For thepurposes of the present invention the term "substituted" as it appliesto R units is the same as defined herein above.

R¹ is an alkoxy unit derived from a fragrance raw material alcohol.Non-limiting examples of preferred fragrance raw material alcoholsinclude 2,4-dimethyl-3-cyclohexene-1-methanol (Floralol), 2,4-dimethylcyclohexane methanol (Dihydro floralol),5,6-dimethyl-1-methylethenylbicyclo [2.2.1]hept-5-ene-2-methanol(Arbozol), α,α-4-trimethyl-3-cyclohexen-1-methanol (α-terpineol),2,4,6-trimethyl-3-cyclohexene-1-methanol (Isocyclo geraniol),4-(1-methylethyl)cyclohexane methanol (Mayol),α-3,3-trimethyl-2-norborane methanol,1,1-dimethyl-1-(4-methylcyclohex-3-enyl)methanol, 2-phenylethanol,2-cyclohexyl ethanol, 2-(o-methylphenyl)-ethanol,2-(m-methylphenyl)ethanol, 2-(p-methylphenyl)ethanol,6,6-dimethylbicyclo-[3.1.1]hept-2-ene-2-ethanol (nopol),2-(4-methylphenoxy)ethanol, 3,3-dimethyl-Δ² -β-norbornane ethanol(patchomint), 2-methyl-2-cyclohexylethanol,1-(4-isopropylcyclohexyl)-ethanol, 1-phenylethanol,1,1-dimethyl-2-phenylethanol, 1,1-dimethyl-2-(4-methyl-phenyl)ethanol,1-phenylpropanol, 3-phenylpropanol, 2-phenylpropanol (HydrotropicAlcohol), 2-(cyclododecyl)propan-1-ol (Hydroxy-ambran),2,2-dimethyl-3-(3-methylphenyl)propan-1-ol (Majantol),2-methyl-3-phenylpropanol, 3-phenyl-2-propen-1-ol (cinnamyl alcohol),2-methyl-3-phenyl-2-propen-1-ol (methylcinnamyl alcohol),(α-n-pentyl-3-phenyl-2-propen-1-ol (α-amyl-cinnamyl alcohol),ethyl-3-hydroxy-3-phenyl propionate, 2-(4-methylphenyl)-2-propanol,3-(4-methylcyclohex-3-ene)butanol,2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)butanol,2-ethyl-4-(2,2,3-trimethyl-cyclopent-3-enyl)-2-buten-1-ol,3-methyl-2-buten-1-ol (prenol),2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, ethyl3-hydroxybutyrate, 4-phenyl-3-buten-2-ol, 2-methyl-4-phenylbutan-2-ol,4-(4-hydroxyphenyl)butan-2-one,4-(4-hydroxy-3-methoxyphenyl)-butan-2-one, 3-methyl-pentanol,3-methyl-3-penten-1-ol, 1-(2-propenyl)cyclopentan-1-ol (plinol),2-methyl-4-phenylpentanol (Pamplefleur), 3-methyl-5-phenylpentanol(Phenoxanol), 2-methyl-5-phenylpentanol,2-methyl-5-(2,3-dimethyltricyclo[2.2.1.0(2,6)]hept-3-yl)-2-penten-1-ol(santalol), 4-methyl-1-phenyl-2-pentanol,5-(2,2,3-trimethyl-3-cyclopentenyl)-3-methylpentan-2-ol (sandalore),(1-methyl-bicyclo[2.1.1]hepten-2-yl)-2-methylpent-1-en-3-ol,3-methyl-1-phenylpentan-3-ol,1,2-dimethyl-3-(1-methylethenyl)cyclopentan-1-ol,2-isopropyl-5-methyl-2-hexenol, cis-3-hexen-1-ol, trans-2-hexen-1-ol,2-isoproenyl-4-methyl-4-hexen-1-ol (Lavandulol),2-ethyl-2-prenyl-3-hexenol, 1-hydroxymethyl-4-iso-propenyl-1-cyclohexene(Dihydrocuminyl alcohol), 1-methyl-4-isopropenylcyclohex-6-en-2-ol(carvenol), 6-methyl-3-isopropenylcyclohexan-1-ol (dihydrocarveol),1-methyl-4-iso-propenylcyclohexan-3-ol,4-isopropyl-1-methylcyclohexan-3-ol, 4-tert-butylcyclo-hexanol,2-tert-butylcyclohexanol, 2-tert-butyl-4-methylcyclohexanol (rootanol),4-isopropyl-cyclohexanol, 4-methyl-1-(1-methylethyl)-3-cyclohexen-1-ol,2-(5,6,6-trimethyl-2-norbomyl)cyclohexanol, isobornylcyclohexanol,3,3,5-trimethylcyclohexanol, 1-methyl-4-isopropylcyclohexan-3-ol,1-methyl-4-isopropylcyclohexan-8-ol (dihydroterpineol),1,2-dimethyl-3-(1-methylethyl)cyclohexan-1-ol, heptanol,2,4-dimethylheptan-1-ol, 6-heptyl-5-hepten-2-ol (isolinalool),2,4-dimethyl-2,6-heptandienol,6,6-dimethyl-2-oxymethyl-bicyclo[3.1.1]hept-2-ene (myrtenol),4-methyl-2,4-heptadien-1-ol, 3,4,5,6,6-pentamethyl-2-heptanol,3,6-dimethyl-3-vinyl-5-hepten-2-ol,6,6-dimethyl-3-hydroxy-2-methylenebicyclo[3.1.1]heptane,1,7,7-trimethylbicyclo[2.2.1 ]heptan-2-ol, 2,6-dimethylheptan-2-ol(dimetol), 2,6,6-trimethylbicyclo[1.3.3]heptan-2-ol, octanol, 2-octenol,2-methyloctan-2-ol, 2-methyl-6-methylene-7-octen-2-ol (myrcenol),7-methyloctan-1-ol, 3,7-dimethyl-6-octenol, 3,7-dimethyl-7-octenol,3,7-dimethyl-6-octen-1-ol (citronellol), 3,7-dimethyl-2,6-octadien-1-ol(geraniol), 3,7-dimethyl-2,6-octadien-1-ol (nerol),3,7-dimethyl-7-methoxyoctan-2-ol (osyrol),3,7-dimethyl-1,6-octadien-3-ol (linalool), 3,7-dimethyloctan-1-ol(pelagrol), 3,7-dimethyloctan-3-ol (tetrahydrolinalool),2,4-octadien-1-ol, 3,7-dimethyl-6-octen-3-ol (dihydrolinalool),2,6-dimethyl-7-octen-2-ol (dihydromyrcenol),2,6-dimethyl-5,7-octadien-2-ol, 4,7-dimethyl-4-vinyl-6-octen-3-ol,3-methyloctan-3-ol, 2,6-dimethyloctan-2-ol, 2,6-dimethyloctan-3-ol,3,6-dimethyloctan-3-ol, 2,6-dimethyl-7-octen-2-ol,2,6-dimethyl-3,5-octadien-2-ol (muguol), 3-methyl-1-octen-3-ol,7-hydroxy-3,7-dimethyloctanal, 3-nonanol, 2,6-nonadien-1-ol,cis-6-nonen-1-ol, 6,8-dimethylnonan-2-ol, 3-(hydroxymethyl)-2-nonanone,2-nonen-1-ol, 2,4-nonadien-1-ol, 3,7-dimethyl-1,6-nonadien-3-ol,decanol, 9-decenol, 2-benzyl-M-dioxa-5-ol, 2-decen-1-ol,2,4-decadien-1-ol, 4-methyl-3-decen-5-ol,3,7,9-trimethyl-1,6-decadien-3-ol (isobutyl linalool), undecanol,2-undecen-1-ol, 10-undecen-1-ol, 2-dodecen-1-ol, 2,4-dodecadien-1-ol,2,7,11-trimethyl-2,6,10-dodecatrien-1-ol (farnesol),3,7,11-trimethyl-1,6,10,-dodecatrien-3-ol (nerolidol),3,7,11,15-tetramethylhexadec-2-en-1-ol (phytol),3,7,11,15-tetramethylhexadec-1-en-3-ol (iso phytol), benzyl alcohol,p-methoxy benzyl alcohol (anisyl alcohol), para-cymen-7-ol (cuminylalcohol), 4-methyl benzyl alcohol, 3,4-methylenedioxy benzyl alcohol,methyl salicylate, benzyl salicylate, cis-3-hexenyl salicylate, n-pentylsalicylate, 2-phenylethyl salicylate, n-hexyl salicylate,2-methyl-5-isopropylphenol, 4-ethyl-2-methoxyphenol,4-allyl-2-methoxyphenol (eugenol), 2-methoxy-4-(1-propenyl)phenol(isoeugenol), 4-allyl-2,6-dimethoxy-phenol, 4-tert-butylphenol,2-ethoxy-4-methylphenol, 2-methyl-4-vinylphenol,2-isopropyl-5-methylphenol (thymol), pentyl-ortho-hydroxy benzoate,ethyl 2-hydroxy-benzoate, methyl 2,4-dihydroxy-3,6-dimethylbenzoate,3-hydroxy-5-methoxy-1-methylbenzene,2-tert-butyl-4-methyl-1-hydroxybenzene,1-ethoxy-2-hydroxy-4-propenylbenzene, 4-hydroxytoluene,4-hydroxy-3-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde,decahydro-2-naphthol, 2,5,5-trimethyloctahydro-2-naphthol,1,3,3-trimethyl-2-norbornanol (fenchol),3a,4,5,6,7,7a-hexahydro-2,4-dimethyl-4,7-methano-1H-inden-5-ol,3a,4,5,6,7,7a-hexahydro-3,4-dimethyl-4,7-methano-1 H-inden-5-ol,2-methyl-2-vinyl-5-(1-hydroxy-1-methylethyl)tetra-hydrofuran,β-caryophyllene alcohol, vanillin, vanillin esters, and mixturesthereof. A listing of common fragrance raw material alcohols can befound in various reference sources, for example, "Perfume and FlavorChemicals", Vols. I and II; Steffen Arctander Allured Pub. Co. (1994)and "Perfumes: Art, Science and Technology"; Muller, P. M. andLamparsky, D., Blackie Academic and Professional (1994) all of which areincorporated herein by reference.

According to the present invention all isomers of a fragrance rawmaterial whether in the form of the pro-fragrance or the releasedfragrance raw material, are suitable for use in the present invention.When optical isomers are possible, fragrance raw materials may beincluded as either the separate chemical isomer or as the combinedracemic mixture. For example, 3,7-dimethyl-6-octen-1-ol, commonly knownby those of ordinary skill in the art as β-citronellol or cephrol,comprises a pair of optical isomers, R-(+)-β-citronellol andS-(-)-p-citronellol. Each of these materials separately or as a racemicpair are suitable for use as fragrance raw materials in the presentinvention. However, those skilled in the art of fragrances, byutilization of the present invention, should not disregard the olfactorydifferences that individual optical isomers, admixtures of opticalisomers or admixtures of positional isomers impart. By way of example,carvone, 2-methyl-5-(1-methylethenyl)-2-cyclohexene-1-one exists as twoisomers; d-carvone and l-carvone. d-Carvone is found in oil of carawayand renders a completely different fragrance from l-carvone which isfound in spearmint oil. According to the present invention apro-fragrance which releases d-carvone will result in a different scentor fragrance than one which releases l-carvone. The same applies tol-carvone. In addition, admixtures of cis/trans isomers, for example,nerol (3,7-dimethyl-cis-2,6-octadien-1-ol) and geraniol(3,7-dimethyl-trans-2,6-octadien-1-ol), are well known to those skilledin the art of perfumery. However, as in the example of geraniol andnerol, the relative amounts of these two isomers in the admixture isimportant when formulating fragrances or perfumes and these ratios mustbe taken into account and adjusted by the formulator.

More preferably, the fragrance raw material alcohol is selected from thegroup consisting of cis-3-hexen-1-ol, hawthanol [admixture of2-(o-methylphenyl)-ethanol, 2-(m-methylphenyl)ethanol, and2-(p-methylphenyl)ethanol], heptan-1-ol, decan-1-ol, 2,4-dimethylcyclohexane methanol, 4-methylbutan-1-ol,2,4,6-trimethyl-3-cyclohexene-1-methanol, 4-(I-methylethyl)cyclohexanemethanol, 3-(hydroxy-methyl)-2-nonanone, octan-1-ol, 3-phenylpropanol,3,7,11,15-tetramethylhexadec-2-en-1-ol (phytol), Rhodinal 70[3,7-dimethyl-7-octenol, 3,7-dimethyl-6-octenol admixture],9-decen-1-ol, α-3,3-trimethyl-2-norborane methanol,3-cyclohexylpropan-1-ol, 3,7-dimethyl-1,6-octadien-3-ol (linalool),4-methyl-1-phenyl-2-pentanol, 3,6-dimethyl-3-vinyl-5-hepten-2-ol, phenylethyl methanol; propyl benzyl methanol,1-methyl-4-isopropenylcyclohexan-3-ol,4-isopropyl-1-methylcyclohexan-3-ol (menthol), 4-tert-butylcyclohexanol,2-tert-butyl-4-methylcyclohexanol, 4-isopropylcyclo-hexanol,trans-decahydro-β-naphthol, 2-tert-butylcyclohexanol,3-phenyl-2-propen-1-ol, 2,7,11-trimethyl-2,6,10-dodecatrien-1-ol,3,7-dimethyl-2,6-octadien-1-ol (geraniol),3,7-dimethyl-2,6-octadien-1-ol (nerol), 4-methoxybenzyl alcohol, benzylalcohol, 4-allyl-2-methoxyphenol, 2-methoxy-4-(1-propenyl)phenol,vanillin, vanillin esters, and mixtures thereof.

Non-limiting examples of ketones which are releasable components of theβ-ketoester pro-fragrances of the present invention include but are notlimited to α-damascone, β-damascone, δ-damascone, β-damascenone,muscone, 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone (cashmeran),cis-jasmone, dihydrojasmone, α-ionone, β-ionone, dihydro-β-ionone,γ-methyl ionone, α-iso-methyl ionone,4-(3,4-methylenedioxyphenyl)butan-2-one, 4-(4-hydroxyphenyl)butan-2-one,methyl β-naphthyl ketone, methyl cedryl ketone,6-acetyl-1,1,2,4,4,7-hexamethyltetralin (tonalid), l-carvone,5-cyclohexadecen-1-one, acetophenone, decatone,2-[2-(4-methyl-3-cyclohexenyl-1-yl)propyl]cyclopentan-2-one,2-sec-butylcyclohexanone, β-dihydro ionone, allyl ionone, α-irone,α-cetone, α-irisone, acetanisole, geranyl acetone,1-(2-methyl-5-isopropyl-2-cyclohexenyl)-1-propanone, acetyldiisoamylene, methyl cyclocitrone, 4-t-pentyl cyclohexanone,p-t-butylcyclohexanone, o-t-butylcyclohexanone, ethyl amyl ketone, ethylpentyl ketone, menthone, methyl-7,3-dihydro-2H-1,5-benzodioxepine-3-one,fenchone, methyl naphthyl ketone, propyl naphthyl ketone, methylhydroxynaphthyl ketone, and mixtures thereof.

More preferably the ketones which are released by the β-ketoesters ofthe present invention are α-damascone, β-damascone, δ-damascone,β-damascenone, muscone, 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone(cashmeran), cis-jasmone, dihydrojasmone, α-ionone, β-ionone,dihydro-β-ionone, γ-methyl ionone, α-iso-methyl ionone,4-(3,4-methylenedioxyphenyl)butan-2-one,4-(4-hydroxyphenyl)-butan-2-one, methyl β-naphthyl ketone, methyl cedrylketone, 6-acetyl-1,1,2,4,4,7-hexamethyltetralin (tonalid), l-carvone,5-cyclohexadecen-1-one, methyl naphthyl ketone, and mixtures thereof.

Non-limiting examples of preferred β-ketoester pro-fragrances include3,7-dimethyl-1,6-octadien-3-yl 3-(β-naphthyl)-3-oxo-propionate, [linalyl(2-naphthoyl)acetate], having the formula: ##STR10##3,7-dimethyl-1,6-octadien-3-yl 3-(α-naphthyl)-3-oxo-propionate, [linalyl(1-naphthoyl)acetate], having the formula: ##STR11##2,6-dimethyl-7-octen-2-yl 3-(4-methoxyphenyl)-3-oxo-propionate,[3-(4-methoxyphenyl)-3-oxo-propionic acid dihydromyrcenyl ester], havingthe formula: ##STR12## 2,6-dimethyl-7-octen-2-yl3-(4-nitrophenyl)-3-oxo-propionate, [3-(4-nitrophenyl)-3-oxo-propionicacid dihydromyrcenyl ester], having the formula: ##STR13##2,6-dimethyl-7-octen-2-yl 3-(β-naphthyl)-3-oxo-propionate,[dihydromyrcenyl (2-naphthoyl)acetate], having the formula: ##STR14##3,7-dimethyl-1,6-octadien-3-yl 3-(4-methoxyphenyl)-3-oxo-propionate,[3-(4-methoxyphenyl)-3-oxo-propionic acid linalyl ester], having theformula: ##STR15## (α,α-4-trimethyl-3-cyclohexenyl)methyl3-(β-naphthyl)-3-oxo-propionate, [α-terpinyl (2-naphthoyl)acetate],having the formula: ##STR16## 9-decen-1-yl3-(β-naphthyl)-3-oxo-propionate, [9-decen-1-yl (2-naphthoyl)acetate],known alternatively as, roslava 2'-acetonaphthone, having the formula:##STR17## 3,7-dimethyl-1,6-octadien-3-yl 3-(nonanyl)-3-oxo-propionate,[linalyl (nonanoyl)acetate], known alternatively as, octyl [(linalyl)α-acetyl] ketone, having the formula: ##STR18##

Further examples of preferred β-ketoester pro-fragrances include3,7-dimethyl-1,6-octadien-3-yl 3-oxo-butyrate, 2,6-dimethyl-7-octen-2-yl3-oxo-butyrate, 6-heptyl-5-hepten-2-yl 3-oxo-butyrate,1-(prop-2-enyl)cyclopentanyl 3-oxo-butyrate,(α,α-4-trimethyl-3-cyclohexenyl)methyl 3-oxo-butyrate, cis-3-hexenyl3-oxo-butyrate, and mixtures thereof.

The β-ketoester pro-fragrances of the present invention are capable ofreleasing a fragrance raw material alcohol and a fragrance raw materialketone depending upon the choice of R and R¹ moieties by the formulator.An example of a released ketone which is not a fragrance raw materialketone is in the case of R equal to methyl and R² and R³ both equal tohydrogen. In this case the released ketone is acetone which is not afragrance raw material as defined herein above.

Depending upon the selection of the R, R², and R³ unit, thesubstantivity of the β-ketoester pro-fragrance can be suitably adjustedby the formulator to provide more or less deposition onto fabric. Thoseskilled in the art of formulating detergent compositions will recognizethat the terms "substantive" and "substantivity" refer to the propensityof a compound to adhere to, associate with, or deposit upon a surface,preferably the surface of fabric. Therefore, compounds which are moresubstantive more readily adhere to fabric surface. However, substantivecompounds, in general, do not react with the surface onto which theydeposit.

As described hereinabove, it has been surprisingly discovered thatpro-fragrances of the present invention, when applied to fabric, breakdown thereby releasing an alcohol and a ketone. For example, thepro-fragrance 3,7-dimethyl-1,6-octadien-3-yl3-(β-naphthyl)-3-oxo-propionate having the formula: ##STR19## breaksdown to release the fragrance raw material alcohol linalool having theformula: ##STR20## and the fragrance raw material ketone methyl naphthylketone having the formula: ##STR21##

A further example includes 2,6-dimethyl-7-octen-2-yl3-(4-methoxyphenyl)-3-oxo-propionate having the formula: ##STR22## whichbreaks down to release the fragrance raw material alcoholdihydromyrcenol having the formula: ##STR23## and methyl 4-methoxyphenylketone having the formula: ##STR24## Fabric Softening Ingredients

The preferred fabric softening agents which comprise the rinse addedfabric softening compositions of the present invention have the formula:##STR25## or the formula: ##STR26## wherein Q is a carbonyl unit havingthe formula: ##STR27## each R unit is independently hydrogen, C₁ -C₆alkyl, C₁ -C₆ hydroxyalkyl, and mixtures thereof, preferably methyl orhydroxy alkyl; each R¹ unit is independently linear or branched C₁₁ -C₂₂alkyl, linear or branched C₁₁ -C₂₂ alkenyl, and mixtures thereof, R² ishydrogen, C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl, and mixtures thereof; X isa cation which is compatible with fabric softener actives and adjunctingredients; the index m is from 1 to 4; the index n is from 1 to 4.

An example of a preferred fabric softener active is a mixture ofquaternized amines having the formula: ##STR28## wherein R is preferablymethyl; R¹ is a linear or branched alkyl or alkenyl chain comprising atleast 11 atoms, preferably at least 15 atoms. In the above fabricsoftener example, the unit --O₂ CR¹ represents a fatty acyl unit whichis typically derived from a triglyceride source. The triglyceride sourceis preferably derived from tallow, partially hydrogenated tallow, lard,partially hydrogenated lard, vegetable oils and/or partiallyhydrogenated vegetable oils, such as, canola oil, safflower oil, peanutoil, sunflower oil, corn oil, soybean oil, tall oil, rice bran oil, etc.and mixtures of these oils.

The preferred fabric softening actives of the present invention are theDiester and/or Diamide Quaternary Ammonium (DEQA) compounds, thediesters and diamides having the formula: ##STR29## wherein R, R¹, X,and n are the same as defined herein above and Q has the formula:##STR30##

These preferred fabric softening actives are formed from the reaction ofan amine with a fatty acyl unit to form an amine intermediate having theformula: ##STR31## wherein R is preferably methyl, Z is --OH, --NH₂, ormixtures thereof; followed by quaternization to the final softeneractive.

Non-limiting examples of preferred amines which are used to form theDEQA fabric softening actives according to the present invention includemethyl bis(2-hydroxyethyl)amine having the formula: ##STR32## methylbis(2-hydroxypropyl)amine having the formula: ##STR33## methyl(3-aminopropyl) (2-hydroxyethyl)amine having the formula: ##STR34##methyl bis(2-aminoethyl)amine having the formula: ##STR35## triethanolamine having the formula: ##STR36## di(2-aminoethyl) ethanolamine havingthe formula: ##STR37##

The counterion, X.sup.(-) above, can be any softener-compatible anion,preferably the anion of a strong acid, for example, chloride, bromide,methylsulfate, ethylsulfate, sulfate, nitrate and the like, morepreferably chloride. The anion can also, but less preferably, carry adouble charge in which case X.sup.(-) represents half a group.

Tallow and canola are convenient and inexpensive sources of fatty acylunits which are suitable for use in the present invention as R¹ units.The following are non-limiting examples of quaternary ammonium compoundssuitable for use in the compositions of the present invention. The term"tallowyl" as used herein below indicates the R¹ unit is derived from atallow triglyceride source and is a mixture of fatty acyl units.Likewise, the use of the term canolyl refers to a mixture of fatty acylunits derived from canola oil.

Table II

Fabric Softener Actives

N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;

N,N-di(canolyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;

N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammoniumchloride;

N,N-di(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammoniumchloride;

N,N-di(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;

N,N-di(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride

N,N-di(2-tallowyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammoniumchloride;

N,N-di(2-canolyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammoniumchloride;

N-(2-tallowoyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethylammonium chloride;

N-(2-canolyloxy-2-ethyl)-N-(2-canolyloxy-2-oxo-ethyl)-N,N-dimethylammonium chloride;

N,N,N-tri(tallowyl-oxy-ethyl)-N-methyl ammonium chloride;

N,N,N-tricanolyl-oxy-ethyl)-N-methyl ammonium chloride;

N-(2-tallowyloxy-2-oxoethyl)-N-(tallowyl)-N,N-dimethyl ammoniumchloride;

N-(2-canolyloxy-2-oxoethyl)-N-(canolyl)-N,N-dimethyl ammonium chloride;

1,2-ditallowyloxy-3-N,N,N-trimethylammoniopropane chloride; and

1,2-dicanolyloxy-3-N,N,N-trimethylammoniopropane chloride;

and mixtures of the above actives.

Particularly preferred is N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethylammonium chloride, where the tallow chains are at least partiallyunsaturated.

The level of unsaturation contained within the tallow, canola, or otherfatty acyl unit chain can be measured by the Iodine Value (IV) of thecorresponding fatty acid, which in the present case should preferably bein the range of from 5 to 100 with two categories of compounds beingdistinguished, having a IV below or above 25.

Indeed, for compounds having the formula: ##STR38## derived from tallowfatty acids, when the Iodine Value is from 5 to 25, preferably 15 to 20,it has been found that a cis/trans isomer weight ratio greater thanabout 30/70, preferably greater than about 50/50 and more preferablygreater than about 70/30 provides optimal concentrability.

For compounds of this type made from tallow fatty acids having a IodineValue of above 25, the ratio of cis to trans isomers has been found tobe less critical unless very high concentrations are needed.

Other suitable examples of fabric softener actives are derived fromfatty acyl groups wherein the terms "tallowyl" and "canolyl" in theabove examples are replaced by the terms "cocoyl, palmyl, lauryl, oleyl,ricinoleyl, stearyl, palmityl," which correspond to the triglyceridesource from which the fatty acyl units are derived. These alternativefatty acyl sources can comprise either fully saturated, or preferably atleast partly unsaturated chains.

As described herein before, R units are preferably methyl, however,suitable fabric softener actives are described by replacing the term"methyl" in the above examples in Table II with the units "ethyl,ethoxy, propyl, propoxy, isopropyl, butyl, isobutyl and t-butyl".

The counter ion, X, in the examples of Table II can be suitably replacedby bromide, methylsulfate, formate, sulfate, nitrate, and mixturesthereof. In fact, the anion, X, is merely present as a counterion of thepositively charged quaternary ammonium compounds. The nature of thecounterion is not critical at all to the practice of the presentinvention. The scope of this invention is not considered limited to anyparticular anion.

The quaternary ammonium or their non-quaternized amine precursorcompounds are present at levels of from about 1% to about 80% ofcompositions herein, depending on the composition execution which can bedilute with a preferred level of active from about 5% to about 15%, orconcentrated, with a preferred level of active from about 15% to about50%, most preferably about 15% to about 35%.

For the preceding fabric softening agents, the pH of the compositionsherein is an important parameter of the present invention. Indeed, itinfluences the stability of the quaternary ammonium or amine precursorscompounds, especially in prolonged storage conditions.

The pH, as defined in the present context, is measured in the neatcompositions at 20° C. While these compositions are operable at pH ofless than about 6.0, for optimum hydrolytic stability of thesecompositions, the neat pH, measured in the above-mentioned conditions,must be in the range of from about 2.0 to about 4.5, preferably about2.0 to about 3.5. The pH of these compositions herein can be regulatedby the addition of a Bronsted acid.

Examples of suitable acids include the inorganic mineral acids,carboxylic acids, in particular the low molecular weight (C₁ -C₅)carboxylic acids, and alkylsulfonic acids. Suitable inorganic acidsinclude HCl, H₂ SO₄, HNO₃ and H₃ PO₄. Suitable organic acids includeformic, acetic, citric, methylsulfonic and ethylsulfonic acid. Preferredacids are citric, hydrochloric, phosphoric, formic, methylsulfonic acid,and benzoic acids.

As used herein, when the diester is specified, it will include themonoester that is normally present in manufacture. For softening, underno/low detergent carry-over laundry conditions the percentage ofmonoester should be as low as possible, preferably no more than about2.5%. However, under high detergent carry-over conditions, somemonoester is preferred. The overall ratios of diester to monoester arefrom about 100:1 to about 2:1, preferably from about 50:1 to about 5:1,more preferably from about 13:1 to about 8:1. Under high detergentcarry-over conditions, the di/monoester ratio is preferably about 1:1.The level of monoester present can be controlled in the manufacturing ofthe softener compound.

Additional Softening Agents

Softening agents which are also useful in the compositions of thepresent invention are nonionic fabric softener materials, preferably incombination with cationic softening agents. Typically, such nonionicfabric softener materials have a HLB of from about 2 to about 9, moretypically from about 3 to about 7. Such nonionic fabric softenermaterials tend to be readily dispersed either by themselves, or whencombined with other materials such as single-long-chain alkyl cationicsurfactant described in detail hereinafter. Dispersibility can beimproved by using more single-long-chain alkyl cationic surfactant,mixture with other materials as set forth hereinafter, use of hotterwater, and/or more agitation. In general, the materials selected shouldbe relatively crystalline, higher melting, (e.g. >40° C.) and relativelywater-insoluble.

The level of optional nonionic softener in the compositions herein istypically from about 0.1% to about 10%, preferably from about 1% toabout 5%.

Preferred nonionic softeners are fatty acid partial esters of polyhydricalcohols, or anhydrides thereof, wherein the alcohol, or anhydride,contains from 2 to 18, preferably from 2 to 8, carbon atoms, and eachfatty acid moiety contains from 12 to 30, preferably from 16 to 20,carbon atoms. Typically, such softeners contain from one to 3,preferably 2 fatty acid groups per molecule.

The polyhydric alcohol portion of the ester can be ethylene glycol,glycerol, poly (e.g., di-, tri-, tetra, penta-, and/or hexa-) glycerol,xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan.Sorbitan esters and polyglycerol monostearate are particularlypreferred.

The fatty acid portion of the ester is normally derived from fatty acidshaving from 12 to 30, preferably from 16 to 20, carbon atoms, typicalexamples of said fatty acids being lauric acid, myristic acid, palmiticacid, stearic acid, oleic and behenic acid.

Highly preferred optional nonionic softening agents for use in thepresent invention are the sorbitan esters, which are esterifieddehydration products of sorbitol, and the glycerol esters.

Commercial sorbitan monostearate is a suitable material. Mixtures ofsorbitan stearate and sorbitan palmitate having stearate/palmitateweight ratios varying between about 10:1 and about 1:10, and1,5-sorbitan esters are also useful.

Glycerol and polyglycerol esters, especially glycerol, diglycerol,triglycerol, and polyglycerol mono- and/or di-esters, preferably mono-,are preferred herein (e.g. polyglycerol monostearate with a trade nameof Radiasurf 7248).

Useful glycerol and polyglycerol esters include mono-esters withstearic, oleic, palmitic, lauric, isostearic, myristic, and/or behenicacids and the diesters of stearic, oleic, palmitic, lauric, isostearic,behenic, and/or myristic acids. It is understood that the typicalmono-ester contains some di- and tri-ester, etc.

The "glycerol esters" also include the polyglycerol, e.g., diglycerolthrough octaglycerol esters. The polyglycerol polyols are formed bycondensing glycerin or epichlorohydrin together to link the glycerolmoieties via ether linkages. The mono- and/or diesters of thepolyglycerol polyols are preferred, the fatty acyl groups typicallybeing those described hereinbefore for the sorbitan and glycerol esters.

Additional fabric softening agents useful herein are described in U.S.Pat. No. 4,661,269, issued Apr. 28, 1987, in the names of Toan Trinh,Errol H. Wahl, Donald M. Swartley, and Ronald L. Hemingway; U.S. Pat.No. 4,439,335, Bums, issued Mar. 27, 1984; and in U.S. Pat. Nos.:3,861,870, Edwards and Diehl; 4,308,151, Cambre; 3,886,075, Bernardino;4,233,164, Davis; 4,401,578, Verbruggen; 3,974,076, Wiersema and Rieke;4,237,016, Rudkin, Clint, and Young; and European Patent Applicationpublication No. 472,178, by Yamamura et al., all of said documents beingincorporated herein by reference.

For the purposes of the present invention, the further suitablesoftening agents which are useful for inclusion in the rinse addedfabric softening compositions of the present invention can be broadlyclassified into one of three general categories:

(a) the reaction product of higher fatty acids with a polyamine selectedfrom the group consisting of hydroxyalkylalkylenediamines anddialkylenetriamines and mixtures thereof (preferably from about 10% toabout 80%); and/or

(b) cationic nitrogenous salts containing only one long chain acyclicaliphatic C₁₅ -C₂₂ hydrocarbon group (preferably from about 3% to about40%); and/or

(c) cationic nitrogenous salts having two or more long chain acyclicaliphatic C₁₅ -C₂₂ hydrocarbon groups or one said group and an arylalkylgroup (preferably from about 10% to about 80%);

with said (a), (b) and (c) preferred percentages being by weight of thefabric softening agent component of the present invention compositions.

Following are the general descriptions of the preceding (a), (b), and(c) softener ingredients (including certain specific examples whichillustrate, but do not limit the present invention).

Component (a)

Softening agents (actives) of the present invention may be the reactionproducts of higher fatty acids with a polyamine selected from the groupconsisting of hydroxyalkylalkylenediamines and dialkylenetriamines andmixtures thereof. These reaction products are mixtures of severalcompounds in view of the multi-functional structure of the polyamines.

The preferred Component (a) is a nitrogenous compound selected from thegroup consisting of the reaction product mixtures or some selectedcomponents of the mixtures. More specifically, the preferred Component(a) is a compound selected from the group consisting of substitutedimidazoline compounds having the formula: ##STR39## wherein R⁷ is anacyclic aliphatic C₁₅ -C₂₁ hydrocarbon group and R⁸ is a divalent C₁ -C₃alkylene group.

Component (a) materials are commercially available as: Mazamide® 6, soldby Mazer Chemicals, or Ceranine® HC, sold by Sandoz Colors & Chemicals;stearic hydroxyethyl imidazoline sold under the trade names of Alkazine®ST by Alkaril Chemicals, Inc., or Schercozoline® S by Scher Chemicals,Inc.; N,N"-ditallowalkoyldiethylenetriamine;1-tallowamidoethyl-2-tallowimidazoline (wherein in the precedingstructure R¹ is an aliphatic C₁₅ -C₁₇ hydrocarbon group and R⁸ is adivalent ethylene group).

Certain of the Components (a) can also be first dispersed in a Bronstedacid dispersing aid having a pKa value of not greater than about 4;provided that the pH of the final composition is not greater than about6. Some preferred dispersing aids are hydrochloric acid, phosphoricacid, or methylsulfonic acid.

Both N,N"-ditallowalkoyldiethylenetriamine and1-tallow(amidoethyl)-2-tallowimidazoline are reaction products of tallowfatty acids and diethylenetriamine, and are precursors of the cationicfabric softening agent methyl-1-tallowamidoethyl-2-tallowimidazoliniummethylsulfate (see "Cationic Surface Active Agents as Fabric Softeners,"R. R. Egan, Journal of the American Oil Chemicals' Society, January1978, pages 118-121). N,N"-ditallow alkoyldiethylenetriamine and1-tallowamidoethyl-2-tallowimidazoline can be obtained from WitcoChemical Company as experimental chemicals.Methyl-1-tallowamidoethyl-2-tallowimidazolinium methylsulfate is sold byWitco Chemical Company under the tradename Varisoft® 475.

Component (b)

The preferred Component (b) is a cationic nitrogenous salt containingone long chain acyclic aliphatic C₁₅ -C₂₂ hydrocarbon group, preferablyselected from acyclic quaternary ammonium salts having the formula:##STR40## wherein R⁹ is an acyclic aliphatic C₁₅ -C₂₂ hydrocarbon group,R¹⁰ and R¹¹ are C₁ -C₄ saturated alkyl or hydroxy alkyl groups, and A-is an anion.

Examples of Component (b) are the monoalkyltrimethylammonium salts suchas monotallowtrimethylammonium chloride, mono(hydrogenatedtallow)trimethylammonium chloride, palmityltrimethyl ammonium chlorideand soyatrimethylammonium chloride, sold by Witco Chemical Company underthe trade name Adogen® 471, Adogen® 441, Adogen® 444, and Adogen® 415,respectively. In these salts, R⁹ is an acyclic aliphatic C₁₆ -C₁₈hydrocarbon group, and R¹⁰ and R¹¹ are methyl groups. Mono(hydrogenatedtallow)trimethylammonium chloride and monotallowtrimethylammoniumchloride are preferred.

Other examples of Component (b) are behenyltrimethylammonium chloridewherein R⁹ is a C₂₂ hydrocarbon group and sold under the trade nameKemamine® Q2803-C by Humko Chemical Division of Witco ChemicalCorporation; soyadimethylethylammonium ethylsulfate wherein R⁹ is a C₁₆-C₁₈ hydrocarbon group, R¹⁰ is a methyl group, R¹¹ is an ethyl group,and A- is an ethylsulfate anion, sold under the trade name Jordaquat®1033 by Jordan Chemical Company; andmethyl-bis(2-hydroxyethyl)-octadecylammonium chloride wherein R⁹ is aC₁₈ hydrocarbon group, R¹⁰ is a 2-hydroxyethyl group and R¹¹ is a methylgroup and available under the trade name Ethoquad® 18/12 from ArmakCompany.

Other examples of Component (b) are 1-ethyl-1-(2-hydroxyethyl)-2-isoheptadecylimidazolinium ethylsulfate, available from MonaIndustries, Inc. under the trade name Monaquat® ISIES;mono(tallowoyloxyethyl) hydroxyethyldimethylammonium chloride, i.e.,monoester of tallow fatty acid with di(hydroxyethyl)dimethylammoniumchloride, a by-product in the process of making diester of tallow fattyacid with di(hydroxyethyl)dimethylammonium chloride, i.e.,di(tallowoyloxyethyl) dimethylammonium chloride.

Component (c)

Preferred cationic nitrogenous salts having two or more long chainacyclic aliphatic C₈ -C₂₂ hydrocarbon groups or one said group and anarylalkyl group which can be used either alone or as part of a mixtureare selected from the group consisting of:

acyclic quaternary ammonium salts having the formula: ##STR41## whereinR¹² is an acyclic aliphatic C₈ -C₂₂ hydrocarbon group, R¹³ is a C₁ -C₄saturated alkyl or hydroxyalkyl group, R¹⁴ is selected from the groupconsisting of R¹² and R¹³ groups, and A- is an anion defined as above.

Examples of Component (c) are the well-known dialkyldi methylammoniumsalts such as ditallowdimethylammonium chloride,ditallowdimethylammonium methylsulfate,di(hydrogenatedtallow)dimethylammonium chloride,distearyldimethylammonium chloride, dibehenyldimethylammonium chloride.Di(hydrogenatedtallow)di methylammonium chloride andditallowdimethylammonium chloride are preferred. Examples ofcommercially available dialkyldimethyl ammonium salts usable in thepresent invention are di(hydrogenatedtallow)dimethylammonium chloride(trade name Adogen® 442), ditallowdimethylammonium chloride (trade nameAdogen® 470), distearyl dimethylammonium chloride (trade name Arosurf®TA-100), all available from Witco Chemical Company.Dibehenyldimethylammonium chloride is sold under the trade name KemamineQ-2802C by Humko Chemical Division of Witco Chemical Corporation.

Other examples of Component (c) aremethylbis(tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate andmethylbis(hydrogenated tallowamidoethyl)(2-hydroxyethyl)ammoniummethylsulfate; these materials are available from Witco Chemical Companyunder the trade names Varisoft® 222 and Varisoft® 110, respectively:dimethylstearylbenzyl ammonium chloride sold under the trade namesVarisoft® SDC by Witco Chemical Company and Ammonyx® 490 by OnyxChemical Company.

An even more preferred composition contains Component (a): the reactionproduct of about 2 moles of hydrogenated tallow fatty acids with about 1mole of N-2-hydroxyethylethylenediamine and is present at a level offrom about 20% to about 70% by weight of the fabric softening componentof the present invention compositions; Component (b): mono(hydrogenatedtallow)trimethyl ammonium chloride present at a level of from about 3%to about 30% by weight of the fabric softening component of the presentinvention compositions; Component (c): selected from the groupconsisting of di(hydrogenatedtallow)dimethylammonium chloride,ditallowdimethylammonium chloride,methyl-1-tallowamidoethyl-2-tallowimidazolinium methylsulfate, diethanolester dimethylammonium chloride, and mixtures thereof; wherein Component(c) is present at a level of from about 20% to about 60% by weight ofthe fabric softening component of the present invention compositions;and wherein the weight ratio of said di(hydrogenatedtallow)dimethylammonium chloride to saidmethyl-1-tallowamidoethyl-2-tallowimidazolinium methylsulfate is fromabout 2:1 to about 6:1.

In the cationic nitrogenous salts described hereinbefore, the anion A-provides charge neutrality. Most often, the anion used to provide chargeneutrality in these salts is a halide, such as chloride or bromide.However, other anions can be used, such as methylsulfate, ethylsulfate,hydroxide, acetate, formate, citrate, sulfate, carbonate, and the like.Chloride and methylsulfate are preferred herein as anion A-.

Liquid Carrier

Another optional, but preferred, ingredient is a liquid carrier. Theliquid carrier employed in the instant compositions is preferably atleast primarily water due to its low cost, relative availability,safety, and environmental compatibility. The level of water in theliquid carrier is preferably at least about 50%, most preferably atleast about 60%, by weight of the carrier. Mixtures of water and lowmolecular weight, e.g., <about 200, organic solvent, e.g., loweralcohols such as ethanol, propanol, isopropanol or butanol are useful asthe carrier liquid. Low molecular weight alcohols include monohydric,dihydric (glycol, etc.) trihydric (glycerol, etc.), and higherpolyhydric (polyols) alcohols.

Additional Solvents

The compositions of the present invention may comprise one or moresolvents which provide increased ease of formulation. This isparticularly the case when formulating liquid, clear fabric softeningcompositions. When employed, the ease of formulation solvent systempreferably comprises less than about 40%, preferably from about 10% toabout 35%, more preferably from about 12% to about 25%, and even morepreferably from about 14% to about 20%, by weight of the composition.The ease of formulation solvent is selected to minimize solvent odorimpact in the composition and to provide a low viscosity to the finalcomposition. For example, isopropyl alcohol is not very effective andhas a strong odor. n-Propyl alcohol is more effective, but also has adistinct odor. Several butyl alcohols also have odors but can be usedfor effective clarity/stability, especially when used as part of a easeof formulation solvent system to minimize their odor. The alcohols arealso selected for optimum low temperature stability, that is they areable to form compositions that are liquid with acceptable lowviscosities and translucent, preferably clear, down to about 40° F.(about 4.4° C.) and are able to recover after storage down to about 20°F. (about 6.7° C.).

The suitability of any ease of formulation solvent for the formulationof the liquid, concentrated, preferably clear, fabric softenercompositions herein with the requisite stability is surprisinglyselective. Suitable solvents can be selected based upon theiroctanol/water partition coefficient (P). Octanol/water partitioncoefficient of a ease of formulation solvent is the ratio between itsequilibrium concentration in octanol and in water. The partitioncoefficients of the ease of formulation solvent ingredients of thisinvention are conveniently given in the form of their logarithm to thebase 10, logP.

The logP of many ingredients has been reported; for example, thePomona92 database, available from Daylight Chemical Information Systems,Inc. (Daylight CIS), Irvine, Calif., contains many, along with citationsto the original literature. However, the logP values are mostconveniently calculated by the "CLOGP" program, also available fromDaylight CIS. This program also lists experimental logP values when theyare available in the Pomona92 database. The "calculated logP" (ClogP) isdetermined by the fragment approach of Hansch and Leo (cf., A. Leo, inComprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J.B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990,incorporated herein by reference). The fragment approach is based on thechemical structure of each ingredient, and takes into account thenumbers and types of atoms, the atom connectivity, and chemical bonding.These ClogP values, which are the most reliable and widely usedestimates for this physicochemical property, are preferably used insteadof the experimental logP values in the selection of the ease offormulation solvent ingredients which are useful in the presentinvention. Other methods that can be used to compute ClogP include,e.g., Crippen's fragmentation method as disclosed in J. Chem. Inf.Comput. Sci., 27, 21 (1987); Viswanadhan's fragmentation method asdisclose in J. Chem. Inf. Comput. Sci., 29, 163 (1989); and Broto'smethod as disclosed in Eur. J. Med. Chem.--Chim. Theor., 19, 71 (1984).

The ease of formulation solvents herein are selected from those having aClogP of from about 0.15 to about 0.64, preferably from about 0.25 toabout 0.62, and more preferably from about 0.40 to about 0.60, said easeof formulation solvent preferably being at least somewhat asymmetric,and preferably having a melting, or solidification, point that allows itto be liquid at, or near room temperature. Solvents that have a lowmolecular weight and are biodegradable are also desirable for somepurposes. The more assymetric solvents appear to be very desirable,whereas the highly symmetrical solvents such as 1 ,7-heptanediol, or1,4-bis(hydroxymethyl) cyclohexane, which have a center of symmetry,appear to be unable to provide the essential clear compositions whenused alone, even though their ClogP values fall in the preferred range.

The most preferred ease of formulation solvents can be identified by theappearance of the softener vesicles, as observed via cryogenic electronmicroscopy of the compositions that have been diluted to theconcentration used in the rinse. These dilute compositions appear tohave dispersions of fabric softener that exhibit a more unilamellarappearance than conventional fabric softener compositions. The closer touni-lamellar the appearance, the better the compositions seem toperform. These compositions provide surprisingly good fabric softeningas compared to similar compositions prepared in the conventional waywith the same fabric softener active.

Operable ease of formulation solvents are disclosed and listed belowwhich have ClogP values which fall within the requisite range. Theseinclude mono-ols, C6 diols, C7 diols, octanediol isomers, butanediolderivatives, trimethylpentanediol isomers, ethylmethylpentanediolisomers, propyl pentanediol isomers, dimethylhexanediol isomers,ethylhexanediol isomers, methylheptanediol isomers, octanediol isomers,nonanediol isomers, alkyl glyceryl ethers, di(hydroxy alkyl) ethers, andaryl glyceryl ethers, aromatic glyceryl ethers, alicyclic diols andderivatives, C₃ C₇ diol alkoxylated derivatives, aromatic diols, andunsaturated diols. Particularly preferred ease of formulation solventsinclude hexanediols such as 1,2-Hexanediol and 2-Ethyl-1,3-hexanedioland pentanediols such as 2,2,4-Trimethyl-1,3-pentanediol. These ease offormulation solvents are all disclosed in copending U.S. patentapplication Ser. Nos. 08/621,019; 08/620,627; 08/620,767; 08/620,513;08/621,285; 08/621,299; 08/621,298; 08/620,626; 08/620,625; 08/620,772;08/621,281; 08/620,514; and 08/620,958, all filed Mar. 22, 1996 and allhaving the title "CONCENTRATED, STABLE, PREFERABLY CLEAR, FABRICSOFTENING COMPOSITION", the disclosures of which are all hereinincorporated by reference.

Concentration Aids

Concentrated compositions of the present invention may require organicand/or inorganic concentration aids to go to even higher concentrationsand/or to meet higher stability standards depending on the otheringredients. Surfactant concentration aids are typically selected fromthe group consisting of single long chain alkyl cationic surfactants;nonionic surfactants; amine oxides; fatty acids; or mixtures thereof,typically used at a level of from 0 to about 15% of the composition.

Inorganic viscosity/dispersibility control agents which can also actlike or augment the effect of the surfactant concentration aids, includewater-soluble, ionizable salts which can also optionally be incorporatedinto the compositions of the present invention. A wide variety ofionizable salts can be used. Examples of suitable salts are the halidesof the Group IA and IIA metals of the Periodic Table of the Elements,e.g., calcium chloride, magnesium chloride, sodium chloride, potassiumbromide, and lithium chloride. The ionizable salts are particularlyuseful during the process of mixing the ingredients to make thecompositions herein, and later to obtain the desired viscosity. Theamount of ionizable salts used depends on the amount of activeingredients used in the compositions and can be adjusted according tothe desires of the formulator. Typical levels of salts used to controlthe composition viscosity are from about 20 to about 20,000 parts permillion (ppm), preferably from about 20 to about 11,000 ppm, by weightof the composition.

Alkylene polyammonium salts can be incorporated into the composition togive viscosity control in addition to or in place of the water-soluble,ionizable salts above. In addition, these agents can act as scavengers,forming ion pairs with anionic detergent carried over from the mainwash, in the rinse, and on the fabrics, and may improve softnessperformance. These agents may stabilize the viscosity over a broaderrange of temperature, especially at low temperatures, compared to theinorganic electrolytes.

Specific examples of alkylene polyammonium salts include 1-lysinemonohydrochloride and 1,5-diammonium 2-methyl pentane dihydrochloride.

Other Ingredients

Still other optional ingredients include, but are not limited to SoilRelease Agents, perfumes, preservatives/stabilizers, chelants,bacteriocides, colorants, optical brighteners, antifoam agents, and thelike.

Soil Release Agents

Soil Release agents are desirably used in fabric softening compositionsof the instant invention. Suitable soil release agents include those ofU.S. Pat. No. 4,968,451, November 6, 1990 to J. J. Scheibel and E. P.Gosselink: such ester oligomers can be prepared by (a) ethoxylatingallyl alcohol, (b) reacting the product of (a) with dimethylterephthalate ("DMT") and 1,2-propylene glycol ("PG") in a two-stagetransesterification/oligomerization procedure and (c) reacting theproduct of (b) with sodium metabisulfite in water; the nonionicend-capped 1,2-propylene/polyoxyethylene terephthalate polyesters ofU.S. Pat. No. 4,711,730, Dec. 8, 1987 to Gosselink et al, for examplethose produced by transesterification/oligomerization ofpoly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol)("PEG"); the partly- and fully-anionic-end-capped oligomeric esters ofU.S. Pat. No. 4,721,580, Jan. 26, 1988 to Gosselink, such as oligomersfrom ethylene glycol ("EG"), PG, DMT andNa-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic-capped blockpolyester oligomeric compounds of U.S. Pat. No. 4,702,857, Oct. 27, 1987to Gosselink, for example produced from DMT, Me-capped PEG and EG and/orPG, or a combination of DMT, EG and/or PG, Me-capped PEG andNa-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl,end-capped terephthalate esters of U.S. Pat. No. 4,877,896, Oct. 31,1989 to Maldonado, Gosselink et al, the latter being typical of SRA'suseful in both laundry and fabric conditioning products, an examplebeing an ester composition made from m-sulfobenzoic acid monosodiumsalt, PG and DMT optionally but preferably further comprising added PEG,e.g., PEG 3400. Another preferred soil release agent is a sulfonatedend-capped type described in U.S. Pat. No. 5,415,807.

Perfumes

While the pro-fragrances of the present invention can be used alone andsimply mixed with essential fabric softening ingredient, most notablysurfactant, they can also be desirably combined into three-partformulations which combine (a) a non-fragranced fabric softening basecomprising one or more synthetic fabric softeners, (b) one or morepro-fragrant β-keto-esters in accordance with the invention and (c) afully-formulated fragrance. The latter provides desirable in-package andin-use (wash-time) fragrance, while the pro-fragrance provides along-term fragrance to the laundered textile fabrics.

In formulating the present fabric softening compositions, thefully-formulated fragrance can be prepared using numerous known odorantingredients of natural or synthetic origin. The range of the natural rawsubstances can embrace not only readily-volatile, but alsomoderately-volatile and slightly-volatile components and that of thesynthetics can include representatives from practically all classes offragrant substances, as will be evident from the following illustrativecompilation: natural products, such as tree moss absolute, basil oil,citrus fruit oils (such as bergamot oil, mandarin oil, etc.), mastixabsolute, myrtle oil, palmarosa oil, patchouli oil, petitgrain oilParaguay, wormwood oil, alcohols, such as farnesol, geraniol, linalool,nerol, phenylethyl alcohol, rhodinol, cinnamic alcohol, aldehydes, suchas citral, Helional™, alpha-hexyl-cinnamaldehyde, hydroxycitronellal,Lilial™ (p-tert-butyl-alpha-methyldihydrocinnamaldehyde),methylnonylacetaldehyde, ketones, such as allylionone, alpha-ionone,beta -ionone, isoraldein (isomethyl-alpha-ionone), methylionone, esters,such as allyl phenoxyacetate, benzyl salicylate, cinnamyl propionate,citronellyl acetate, citronellyl ethoxolate, decyl acetate,dimethylbenzylcarbinyl acetate, dimethylbenzylcarbinyl butyrate, ethylacetoacetate, ethyl acetylacetate, hexenyl isobutyrate, linalyl acetate,methyl dihydrojasmonate, styrallyl acetate, vetiveryl acetate, etc.,lactones, such as gamma-undecalactone, various components often used inperfumery, such as musk ketone, indole, p-menthane-8-thiol-3-one, andmethyl-eugenol. Likewise, any conventional fragrant acetal or ketalknown in the art can be added to the present composition as an optionalcomponent of the conventionally formulated perfume (c). Suchconventional fragrant acetals and ketals include the well-known methyland ethyl acetals and ketals, as well as acetals or ketals based onbenzaldehyde, those comprising phenylethyl moieties, or more recentlydeveloped specialties such as those described in a United States patententitled "Acetals and Ketals of Oxo-Tetralins and Oxo-Indanes", see U.S.Pat. No. 5,084,440, issued Jan. 28, 1992, assigned to Givaudan Corp. Ofcourse, other recent synthetic specialties can be included in theperfume compositions for fully-formulated fabric softening compositions.These include the enol ethers of alkyl-substituted oxo-tetralins andoxo-indanes as described in U.S. Pat. No. 5,332,725, Jul. 26, 1994,assigned to Givaudan; or Schiff Bases as described in U.S. Pat. No.5,264,615, Dec. 9, 1991, assigned to Givaudan. It is preferred that thepro-fragrant material be added separately from the conventionalfragrances to the fabric softening compositions of the invention.

Stabilizers

Stabilizers can be present in the compositions of the present invention.The term "stabilizer," as used herein, includes antioxidants andreductive agents. These agents are present at a level of from 0% toabout 2%, preferably from about 0.01% to about 0.2%, more preferablyfrom about 0.035% to about 0.1% for antioxidants, and more preferablyfrom about 0.01% to about 0.2% for reductive agents. These assure goododor stability under long term storage conditions for the compositionsand compounds stored in molten form. The use of antioxidants andreductive agent stabilizers is especially critical for low scentproducts (low perfume).

Examples of antioxidants that can be added to the compositions of thisinvention include a mixture of ascorbic acid, ascorbic palmitate, propylgallate, available from Eastman Chemical Products, Inc., under the tradenames Tenox® PG and Tenox S-1; a mixture of BHT (butylatedhydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, andcitric acid, available from Eastman Chemical Products, Inc., under thetrade name Tenox-6; butylated hydroxytoluene, available from UOP ProcessDivision under the trade name Sustane® BHT; tertiary butylhydroquinone,Eastman Chemical Products, Inc., as Tenox TBHQ; natural tocopherols,Eastman Chemical Products, Inc., as Tenox GT-1/GT-2; and butylatedhydroxyanisole, Eastman Chemical Products, Inc., as BHA; long chainesters (C₈ -C₂₂) of gallic acid, e.g., dodecyl gallate; Irganox® 1010;Irganox® 1035; Irganox® B 1171; Irganox® 1425; Irganox® 3114; Irganox®3125; and mixtures thereof; preferably Irganox® 3125, Irganox® 1425,Irganox® 3114, and mixtures thereof; more preferably Irganox® 3125 aloneor mixed with citric acid and/or other chelators such as isopropylcitrate, Dequest® 2010, available from Monsanto with a chemical name of1-hydroxyethylidene-1,1-diphosphonic acid (etidronic acid), and Tiron®,available from Kodak with a chemical name of4,5-dihydroxy-m-benzene-sulfonic acid/sodium salt, EDDS, and DTPA®,available from Aldrich with a chemical name ofdiethylenetriaminepentaacetic acid. The chemical names and CAS numbersfor some of the above stabilizers are listed in Table II below.

                  TABLE II                                                        ______________________________________                                                             Chemical Name used in Code of                            Antioxidant                                                                              CAS No.   Federal Regulations                                      ______________________________________                                        Irganox ® 1010                                                                       6683-19-8 Tetrakis (methylene(3,5-di-tert-butyl-                                        4hydroxyhydrocinnamate))methane                          Irganox ® 1035                                                                       41484-35-9                                                                              Thiodiethylene bis(3,5-di-tert-butyl-                                         4-hydroxyhydrocinnamate                                  Irganox ® 1098                                                                       23128-74-7                                                                              N,N'-Hexamethylene bis(3,5-di-                                                tert-butyl-4-hydroxyhydro-                                                    cinnamamide                                              Irganox ® B 1171                                                                     31570-04-4                                                                              1:1 Blend of Irganox ® 1098 and                                 23128-74-7                                                                              Irgafos ® 168                                        Irganox ® 1425                                                                       65140-91-2                                                                              Calcium bis(monoethyl(3,5-di-                                                 tert-butyl-4-hydroxybenzyl)-                                                  phosphonate)                                             Irganox ® 3114                                                                       65140-91-2                                                                              Calcium bis(monoethyl(3,5-di-                                                 tert-butyl-4-hydroxybenzyl)-                                                  phosphonate)                                             Irganox ® 3125                                                                       34137-09-2                                                                              3,5-Di-tert-butyl-4-hydroxy-                                                  hydrocinnamic acid triester                                                   with 1,3,5-tris(2-hydroxyethyl)-S-                                            triazine-2,4,6-(1H, 3H, 5H)-trione                       Irgafos ® 168                                                                        31570-04-4                                                                              Tris(2,4-di-tert-butyl-phenyl)-                                               phosphite                                                ______________________________________                                    

Examples of reductive agents include sodium borohydride, hypophosphorousacid, Irgafos® 168, and mixtures thereof.

The following examples illustrate the β-keto-esters and compositions ofthis invention, but are not intended to be limiting thereof.

EXAMPLE 1 Preparation of 3,7-Dimethyl-1,6-octadien-3-yl3-(β-naphthyl-3-oxo-propionate

Lithium diisopropylamide (101.0 mL of a 2.0M solution, 0.202 mol) isplaced into a 500 mL three-necked round-bottomed flask fitted with amagnetic stirrer, internal thermometer, argon inlet, and additionfunnel. The flask is placed in a dry ice-acetone bath.3,7-Dimethyl-1,6-octadien-3-yl acetate (linalyl acetate) in the amountof (18.66 g, 0.095 mol) is dissolved in THF (5 mL) and the resultingsolution added to the flask over 45 min. Once addition is complete, themixture is stirred for an additional 15 min before being treated with asolution of 2-naphthoyl chloride in the amount of (17.43 g, 0.090 mol)dissolved in THF (25 mL) over 30 min. The mixture is warmed to -20° C.and stirred at that temperature for 18 h. After warming to 0° C., themixture is quenched with 20% HCl (53 mL). The mixture is poured into aseparatory funnel containing ether (150 mL) and water (250 mL). Theaqueous layer is extracted with ether (150 mL). The combined organiclayers are washed with saturated NaHCO₃ solution (2×100 mL), water(2×150 mL) and brine (150 mL), dried over MgSO₄ and filtered. Thesolvent is removed by rotary evaporation to give an orange/red oil. Theoil is purified by column chromatography (elution with 5% ethyl acetatedissolved in petroleum ether) to give an oil. Purity of the product isdetermined by thin layer chromatography and GC analysis and thestructure confirmed by mass spectrometry, ¹ H and ¹³ C NMR.

EXAMPLE 2 Preparation of 2,6-Dimethyl-7-octen-2-yl3-(4-Methoxyphenyl)-3-oxo-propionate

N-Isopropylcyclohexylamine (25.00 g, 0.177 mol) and THF in the amount of200 mL is placed into a 1000 mL three-necked round-bottomed flask fittedwith a magnetic stirrer, internal thermometer, argon inlet, and additionfunnel. The flask is placed in a ice-methanol bath cooled to -5° C. andits contents treated with n-butyllithium in the amount of (70.8 mL of a2.50 M solution, 0.177 mol). The mixture is stirred for 20 min and thencooled to -78° C. 2,6-Dimethyl-7-octen-2-yl acetate (dihydromyrcenylacetate) in the amount of (17.55 g, 0.089 mol) is dissolved in THF (10mL) and the resulting solution added to the flask over 45 min. Onceaddition is complete, the mixture is stirred for an additional 15 minbefore being treated with a solution of p-methoxybenzoyl chloride in theamount of (15.10 g, 0.090 mol) dissolved in THF (25 ml) over 30 min andthen stirred for 1 h. The mixture is warmed to 0° C. and then treatedwith 90 mL of 20% HCl an hour later. The mixture is poured into aseparatory funnel containing ether (100 ml) and water (200 ml). Theaqueous layer is extracted with ether (100 ml). The combined organiclayers are washed with saturated NaHCO₃ solution (2×100 ml), water(2×100 ml) and brine (100 ml), dried over MgSO₄ and filtered. Thesolvent is removed by rotary evaporation to give an orange/red oil. Theoil is purified by column chromatography (elution with 5% ethyl acetatedissolved in petroleum ether) to give an oil. Purity of the product isdetermined by thin layer chromatography and the structure confirmed by ¹H and ¹³ C NMR.

EXAMPLE 3 Preparation of 2,6-Dimethyl-7-octen-2-yl3-(4-nitrophenyl)-3-oxo-propionate

Lithium diisopropylamide (121.0 mL of a 2.0M solution, 0.243 mol) isplaced into a 500 mL three-necked round-bottomed flask fitted with amagnetic stirrer, internal thermometer, argon inlet, and additionfunnel. The flask is placed in a dry ice-acetone bath.2,6-Dimethyl-7-octen-2-yl acetate (22.66 g, 0.114 mol) is dissolved inTHF (5 mL) and the resulting solution added to the flask over 45 min.Once addition is complete, the mixture is stirred for an additional 15min. before being treated with a solution of 4-nitrobenzoyl chloride(20.00 g, 0.108 mol) dissolved in THF (25 mL) over 30 min. The mixtureis warned to -20° C. and stirred at that temperature for 18 h. Afterwarming to 0° C., the mixture is quenched with 20% HCl (70 mL). Themixture is poured into a separatory funnel containing ether (150 mL) andwater (250 mL). The aqueous layer is extracted with ether (150 mL). Thecombined organic layers are washed with saturated NaHCO₃ solution (2×100mL), water (2×150 mL) and brine (150 mL), dried over MgSO₄ and filtered.The solvent is removed by rotary evaporation to give an orange/red oil.The oil is purified by column chromatography (elution with 2% ethylacetate/petroleum ether) to yield a colorless oil having ¹ H and ¹³ CNMR spectra consistent with the desired product.

EXAMPLE 4 Preparation of 2,6-Dimethyl-7-octen-2-yl3-(β-naphthyl)-3-oxo-propionate

Lithium diisopropylamide in the amount of (100.0 mL of a 2.0 M solution,0.201 mol) is placed into a 500 mL three-necked round-bottomed flaskfitted with a magnetic stirrer, internal thermometer, argon inlet, andaddition funnel. The flask is cooled to -78° C.2,6-Dimethyl-7-octen-2-yl acetate in the amount of (18.75 g, 0.095 mol)is dissolved in THF (5 mL) and the resulting solution added to the flaskover 45 min. Once addition is complete, the mixture is stirred for anadditional 15 min before being treated with a solution of 2-naphthoylchloride in the amount of (17.00 g, 0.089 mol) dissolved in THF (25 mL)over 30 min. The mixture is warmed to -20° C. and stirred at thattemperature for 18 h. After warming to 0° C., the mixture is quenchedwith 20% HCl (55 mL). The mixture is poured into a separatory funnelcontaining ether (150 mL) and water (250 mL). The aqueous layer isextracted with ether (150 mL). The combined organic layers are washedwith saturated NaHCO₃ solution (2×100 mL), water (2×150 mL) and brine(150 mL), dried over MgSO₄ and filtered. The solvent is removed byrotary evaporation to give an orange/red oil. The oil is purified bycolumn chromatography (elution with 2% ethyl acetate dissolved inpetroleum ether) to give an oil. Purity of the product is determined bythin layer chromatography and the structure confirmed by ¹ H and ¹³ CNMR.

EXAMPLE 5 Preparation of 3,7-Dimethyl-1,6-octadien-3-yl3-(4-Methoxyphenyl)-3-oxo-propionate

Lithium diisopropylamide (119.0 mL of a 2.0M solution, 0.238 mol) isplaced into a 500 mL three-necked round-bottomed flask fitted with amagnetic stirrer, internal thermometer, argon inlet, and additionfunnel. The flask is cooled to -78° C. 3,7-dimethyl-1,6-octadien-3-ylacetate (22.04 g, 0.112 mol) is dissolved in THF (5 mL) and theresulting solution added to the flask over 45 min. Once addition iscomplete, the mixture is stirred for an additional 15 min. before beingtreated with a solution of p-anisoyl chloride (35.00 g, 0.106 mol)dissolved in THF (30 mL) over 30 min. The mixture is warmed to -20° C.and stirred at that temperature for 18 h. After warming to 0° C., themixture is quenched with 20% HCl (80 mL). The mixture is poured into aseparatory funnel containing ether (150 mL) and water (250 mL). Theaqueous layer is extracted with ether (150 mL). The mixture is pouredinto a separatory funnel containing ether (150 mL) and water (250 mL).The aqueous layer is extracted with ether (150 mL). The combined organiclayers are washed with saturated NaHCO₃ solution (2×100 mL), water(2×150 mL) and brine (150 mL), dried over MgSO₄ and filtered. Thesolvent is removed by rotary evaporation to give an oil. The oil ispurified by column chromatography (elution with 2% ethylacetate/petroleum ether) to yield a colorless oil having ¹ H and ¹³ CNMR spectra consistent with the desired product.

EXAMPLE 6 Preparation of (α,α-4-Trimethyl-3-cyclohexenyl)methyl3-(β-naphthyl)-3-oxo-propionate

Lithium diisopropylamide (171.0 mL of a 2.0M solution, 0.342 mol) isplaced into a 1000 mL three-necked round-bottomed flask fitted with amagnetic stirrer, internal thermometer, argon inlet, and additionfunnel. The flask is cooled to -78° C.(α,α-4-Trimethyl-3-cyclohexenyl)methyl acetate (30.00 g, 0.153 mol) isdissolved in THF (10 mL) and the resulting solution added to the flaskover 45 min. Once addition is complete, the mixture is stirred for anadditional 15 min. before being treated with a solution of 2-naphthoylchloride (29.00 g, 0.152 mol) dissolved in THF (50 mL) over 30 min. Themixture is warmed to -20° C. and stirred at that temperature for 18 h.After warming to 0° C., the mixture is quenched with 20% HCl (105 mL).The mixture is poured into a separatory funnel containing ether (150 mL)and water (250 mL). The mixture is poured into a separatory funnelcontaining ether (150 mL) and water (250 mL). The aqueous layer isextracted with ether (150 mL). The combined organic layers are washedwith saturated NaHCO₃ solution (2×100 mL), water (2×150 mL) and brine(150 mL), dried over MgSO₄ and filtered. The solvent is removed byrotary evaporation to give an oil. The oil is purified by columnchromatography (elution with 2% ethyl acetate/petroleum ether) to yielda semi-white solid which is triturated in cold n-pentane to yield awhite powder having ¹ H and ¹³ C NMR spectra consistent with the desiredproduct.

EXAMPLE 7 Preparation of 3,7-Dimethyl-1,6-octadien-3-yl3-(α-Naphthyl)-3-oxo-propionate

Lithium diisopropylamide (96.3 mL of a 2.0M solution, 0.193 mol) isplaced into a 500 mL three-necked round-bottomed flask fitted with amagnetic stirrer, internal thermometer, argon inlet, and additionfunnel. The flask is cooled to -78° C. 3,7-dimethyl-1,6-octadien-3-ylacetate (17.81 g, 0.091 mol) is dissolved in THF (5 mL) and theresulting solution added to the flask over 45 min. Once addition iscomplete, the mixture is stirred for an additional 15 min. before beingtreated with a solution of 1-naphthoyl chloride (16.82 g, 0.086 mol)dissolved in THF (25 mL) over 30 min. The mixture is warmed to -20° C.and stirred at that temperature for 18 h. After warming to 0° C., themixture is quenched with 20% HCl (53 mL). The mixture is poured into aseparatory funnel containing ether (150 mL) and water (250 mL). Theaqueous layer is extracted with ether (150 mL). The combined organiclayers are washed with saturated NaHCO₃ solution (2×100 mL), water(2×150 mL) and brine (150 mL), dried over MgSO₄ and filtered. Thesolvent is removed by rotary evaporation to give an oil. The oil ispurified by column chromatography (elution with 2% ethylacetate/petroleum ether) to yield a colorless oil having ¹ H and ¹³ CNMR spectra consistent with the desired product.

EXAMPLE 8 Preparation of cis 3-Hexen-1-yl3-(β-Naphthyl)-3-oxo-propionate

Lithium diisopropylamide (133.0 mL of a 2.0M solution, 0.266 mol) isplaced into a 500 mL three-necked round-bottomed flask fitted with amagnetic stirrer, internal thermometer, argon inlet, and additionfunnel. The flask is cooled to -78° C. cis 3-Hexenyl acetate (17.80 g,0.125 mol) is dissolved in THF (10 mL) and the resulting solution addedto the flask over 45 min. Once addition is complete, the mixture isstirred for an additional 15 min. before being treated with a solutionof 2-naphthoyl chloride (22.51 g, 0.118 mol) dissolved in THF (30 mL)over 30 min. The mixture is warmed to -20° C. and stirred at thattemperature for 18 h. After warming to 0° C., the mixture is quenchedwith 20% HCl (70 mL). The mixture is poured into a separatory funnelcontaining ether (150 mL) and water (250 mL). The aqueous layer isextracted with ether (150 mL). The combined organic layers are washedwith saturated NaHCO₃ solution (2×100 mL), water (2×150 mL) and brine(150 mL), dried over MgSO₄ and filtered. The solvent is removed byrotary evaporation to give an orange/red oil. The oil is purified bycolumn chromatography (elution with 2% ethyl acetate/petroleum ether) toyield a colorless oil having ¹ H and ¹³ C NMR spectra consistent withthe desired product.

EXAMPLE 9 Preparation of 9-Decen-1-yl 3-(β-Naphthyl)-3-oxo-propionate

Lithium diisopropylamide (79.8 mL of a 2.0M solution, 0.160 mol) isplaced into a 250 mL three-necked round-bottomed flask fitted with amagnetic stirrer, internal thermometer, argon inlet, and additionfunnel. The flask is cooled to -78° C. 9-Decen-1-yl acetate (14.91 g,0.075 mol) is dissolved in THF (5 mL) and the resulting solution addedto the flask over 45 min. Once addition is complete, the mixture isstirred for an additional 15 min. before being treated with a solutionof 2-naphthoyl chloride (13.80 g, 0.071 mol) dissolved in THF (25 mL)over 30 min. The mixture is warmed to -20° C. and stirred at thattemperature for 18 h. After warming to 0° C., the mixture is quenchedwith 20% HCl (47 mL). The mixture is poured into a separatory funnelcontaining ether (150 mL) and water (250 mL). The aqueous layer isextracted with ether (150 mL). The combined organic layers are washedwith saturated NaHCO₃ solution (2×100 mL), water (2×150 mL) and brine(150 mL), dried over MgSO₄ and filtered. The solvent is removed byrotary evaporation to give an orange/red oil. The oil is purified bycolumn chromatography (elution with 2% ethyl acetate/petroleum ether) toyield a colorless oil having ¹ H and ¹³ C NMR spectra consistent withthe desired product.

EXAMPLE 10 Preparation of 3,7-Dimethyl-1,6-octadien-3-yl3-(Nonanyl)-3-oxo-propionate

Lithium diisopropylamide (133.7 mL of a 2.0M solution, 0.267 mol) isplaced into a 500 mL three-necked round-bottomed flask fitted with amagnetic stirrer, internal thermometer, argon inlet, and additionfunnel. The flask is cooled to -78° C. 3,7-dimethyl-1,6-octadien-3-ylacetate (24.73 g, 0.126 mol) is dissolved in THF (40 mL) and theresulting solution added to the flask over 45 min. Once addition iscomplete, the mixture is stirred for an additional 15 min. before beingtreated with a solution of nonanoyl chloride (21.88 g, 0.119 mol) over30 min. The mixture is warmed to -20° C. and stirred at that temperaturefor 18 h. After warming to 0° C., the mixture is quenched with 20% HCl(60 mL). The mixture is poured into a separatory funnel containing ether(150 mL) and water (250 mL). The aqueous layer is extracted with ether(150 mL). The combined organic layers are washed with saturated NaHCO₃solution (2×100 mL), water (2×150 mL) and brine (150 mL), dried overMgSO₄ and filtered. The solvent is removed by rotary evaporation to givean orange/red oil. The oil is purified by column chromatography (elutionwith 2% ethyl acetate/petroleum ether) to yield a colorless oil having ¹H and ¹³ C NMR spectra consistent with the desired product.

EXAMPLE 11 Preparation of 2,6-Dimethyl-7-octen-2-yl3-(Nonanyl)-3-oxo-propionate

Lithium diisopropylamide (75.7 mL of a 2.0M solution, 0.151 mol) isplaced into a 500 mL three-necked round-bottomed flask fitted with amagnetic stirrer, internal thermometer, argon inlet, and additionfunnel. The flask is cooled to -78° C. 2,6-Dimethyl-7-octen-2-yl acetate(14.14 g, 0.071 mol) is dissolved in THF (20 mL) and the resultingsolution added to the flask over 45 min. Once addition is complete, themixture is stirred for an additional 15 min. before being treated with asolution of nonanoyl chloride (12.38 g, 0.067 mol) over 30 min. Themixture is warmed to -20° C. and stirred at that temperature for 18 h.After warming to 0° C., the mixture is quenched with 20% HCl (55 mL).The mixture is poured into a separatory funnel containing ether (150 mL)and water (250 mL). The aqueous layer is extracted with ether (150 mL).The combined organic layers are washed with saturated NaHCO₃ solution(2×100 mL), water (2×150 mL) and brine (150 mL), dried over MgSO₄ andfiltered. The solvent is removed by rotary evaporation to give anorange/red oil. The oil is purified by column chromatography (elutionwith 2% ethyl acetate/petroleum ether) to yield a colorless oil having ¹H and ¹³ C NMR spectra consistent with the desired product.

EXAMPLE 12 Preparation of 3,7-Dimethyl-1,6-octadien-3-yl 3-Oxo-butyrate

A mixture of linalool (100 g, 0.648 mol) and 4-dimethylaminopyridine(0.40 g, 3.20 mmol) in a 500 mL three-necked round-bottomed flask fittedwith a condenser, argon inlet, addition funnel, magnetic stirrer andinternal thermometer is heated to 55° C. Diketene (54.50 g, 0.648 mol)is added dropwise in the course of 30 min. The mixture has a slightexotherm and turns from yellow to red during this time. After stirringan additional hour at 50° C., the mixture is cooled to room temperature.At this point, NMR analysis indicates the reaction is complete. Thematerial from this lot is carried onto the next step. Purification of anearlier sample from this route by flash chromtography (elution withdichloromethane) yields the desired product in 92% yield and nearlycolorless.

EXAMPLE 13 Preparation of 2,6-Dimethyl-7-octen-2-yl 3-Oxo-butyrate

A mixture of dihydromyrcenol (37.88 g, 0.240 mol) and4-dimethylaminopyridine (0.16 g, 1.30 mmol) in a 100 mL three-neckedround-bottomed flask fitted with a condenser, argon inlet, additionfunnel, magnetic stirrer and internal thermometer is heated to 50-60° C.Diketene (20.16 g, 0.240 mol) is added dropwise in the course of 15 min.The mixture has a slight exotherm and turned from yellow to red duringthis time. After stirring an additional hour at 50 C, the mixture iscooled to room temperature. At this point, NMR analysis indicates thereaction is complete. Purification of the product mixture by flashchromatography (elution with dichloromethane) yields the desired productin 95% yield as a nearly colorless oil.

EXAMPLE 14 Preparation of 3,7-Dimethyl-1,6-octadien-3-yl3-(β-Naphthyl)-3-oxo-propionate

Crude 3,7-dimethyl-1,6-octadien-3-yl 3-oxo-butyrate (154.51, 0.648 mol)from above is placed in a 3000 mL three-necked round-bottomed flaskfitted with a condenser, argon inlet, addition funnel, magnetic stirrerand internal thermometer. The contents are dissolved in 350 mL ofdichloromethane and treated with powdered calcium hydroxide (50.44 g,0.681 mol). The mixture is stirred at 30° C. for 30 min and then heatedto 40° C. 2-Naphthoyl chloride (142.12 g, 0.746 mol) dissolved in 20 mLof dichloromethane is added dropwise over 15 min. The mixture continuesto be heated at this temperature for 1 h. Ammonium chloride (36.41 g,0.681 mol) dissolved in 250 mL of water is added to the reaction mixtureand the pH adjusted to ˜9 with 28% ammonium hydroxide. After stirring 30min at 35° C. the pH is adjusted to ˜1 with 20% HCl. The mixture istransferred to a separatory funnel containing diethyl ether (500 mL) andwater (500 mL). The layers are separated and the organic phase is washedwith saturated NaHCO₃ solution (2×500 mL), dried over MgSO₄, filteredand concentrated by rotary evaporation to give a yellow red oil. At thispoint a light yellow solid precipitates from the mixture. An equalvolume of hexane is added and the solids is collected by filtration anddried. NMR analysis indicates the solid is 2-naphthoic acid. The eluentis concentrated again by rotary evaporation to give a red oil. The oilis taken up in an equal volume of dichloromethane, passed through a plugof silica gel (400 g) and eluted with dichloromethane. The mixture isconcentrated by rotary evaporation and stripped by Kugelrohrdistillation (40° C., 0.10 mm Hg, 30 min) to yield 173.26 g (76.3%) ofthe product as a red oil; this product is a mixture of a 1:10 molarratio of linalyl acetoacetate to linalyl (2-naphthoyl)acetate. A portionof this material is purified by column chromatography (elution with 2.5%ethyl acetate in hexanes) to give the desired product as a light yellowoil.

EXAMPLE 15 Preparation of 3,7-Dimethyl-1,6-octadien-3-yl3-(β-Naphthyl)-3-oxo-2,2-dimethylpropionate

Sodium hydride (2.30 g, 0.057 mol, 60%) and tetrahydrofuran (50 mL) areplaced into a 250 mL three-necked round-bottomed flask fitted with amagnetic stirrer, ice bath, addition funnel, internal thermometer andargon inlet. The contents of the flask are cooled to 0° C.3,7-Dimethyl-1,6-octadien-3-yl 3-(β-naphthyl)-3-oxo-propionate (8.94 g,0.025 mol) dissolved in 50 mL of tetrahydrofuran is added dropwise tothe flask over 30 min. During addition, the mixture evolves gas. Afterstirring for 1 h, methyl iodide (7.24 g, 0.051 mol) is added to thereaction mixture. Stirring continues for 2 h at 0° C. and then at roomtemperature for 18 h. The mixture is neutralized with 20% HCl andextracted with diethyl ether. The organic layers are washed withsaturated NaHCO₃ solution, water, dried over MgSO₄, filtered,concentrated by rotary evaporation and purified by flash chromatographyto yield the desired compound. Structure is confirmed my ¹ H and ¹³ CNMR.

EXAMPLE 16 Preparation of 3,7-Dimethyl-1,6-octadien-3-yl3-(β-naphthyl-3-oxo-2-methylpropionate

Sodium hydride (3.92 g, 0.098 mol, 60%) and tetrahydrofuran (100 mL) areplaced into a 250 mL three-necked round-bottomed flask fitted with amagnetic stirrer, ice bath, addition funnel, internal thermometer andargon inlet. The contents of the flask are cooled to 0° C.3,7-Dimethyl-1,6-octadien-3-yl 3-(β-naphthyl)-3-oxo-propionate (15.28 g,0.044 mol) dissolved in 50 mL of tetrahydrofuran is added dropwise tothe flask over 30 min. During addition, the mixture evolves gas. Afterstirring for 1 h, methyl iodide (10.65 g, 0.075 mol) is added to thereaction mixture. Stirring continues for 2 h at 0° C. and then at roomtemperature for 18 h. The mixture is neutralized with 20% HCl andextracted with diethyl ether. The organic layers are washed withsaturated NaHCO₃ solution, water, dried over MgSO₄, filtered,concentrated by rotary evaporation and purified by flash chromatographyto yield the desired compound. Structure is confirmed my ¹ H and ¹³ CNMR.

EXAMPLE 17 Preparation of 3,7-Dimethyl-1,6-octadien-3-yl3-(Hexyl)-3-oxo-propionate

3,7-Dimethyl-1,6-octadien-3-yl 3-oxo-butyrate (30.00 g, 0.126 mol),dichloromethane (50 mL) and methyl ethyl ketone (10 mL) are combined ina 500 mL three-necked round-bottomed flask fitted with an internalthermometer, addition funnel, condenser and argon inlet. Calciumhydroxide (9.80 g, 0.132 mol, powdered) is added to the flask and theslurry stirs for 1 h. Heptanoyl chloride (17.84 g, 0.120 mol) in 10 mlof dichloromethane is added over 15 min so as to keep the reactiontemperature between 35-40° C. The reaction continues to stir at 35-40°C. for 2 h. Ammonium chloride (7.06 g, 0.132 mol) dissolved in 20 mL ofwater is added to the flask. After 20 min, concentrated ammoniumhydroxide is added to the mixture to adjust the pH to ˜9.0. After 1 h,20% HCl solution is added to drop the pH to ˜1.0. After 1 h, the mixtureis poured into 300 mL of dichloromethane. The layers are separated andthe aqueous phase extracted with 100 mL of dichloromethane. The combineorganic layers are washed with saturated NaHCO₃ solution, water, driedover MgSO₄, filtered, concentrated by rotary evaporation and purified byflash chromatography to yield the desired compound. Structure isconfirmed my ¹ H and ¹³ C NMR.

EXAMPLE 18 Preparation of 3,7-Dimethyl-1,6-octadien-3-yl3-Oxo-2-benzylbutyrate

Potassium carbonate (3.92 g, 0.028 mol), 3,7-dimethyl-1,6-octadien-3-yl3-oxo-butyrate (4.80 g, 0.030 mol), benzyl chloride (4.80 g, 0.038 mol)and acetone (15 mL) are placed in a 50 mL round-bottomed flask fittedwith a magnetic stirrer, condenser and argon inlet. The mixture isheated to reflux for 18 h. The cooled mixture is filtered andconcentrated by rotary evaporation. The resulting oil is purified onsilica gel to yield the desired compound. Structure is confirmed by thinlayer chromatography and ¹ H and ¹³ C NMR.

Examples of Liquid Fabric Softener Compositions Containing β-Keto-EsterPro-perfumes

    ______________________________________                                        Formulation                                                                   Example: A       B       C     D     E     F                                  Ingredient                                                                             Wt. %   Wt. %   Wt. % Wt. % Wt. % Wt. %                              ______________________________________                                        DEQA.sup.1                                                                             25.0    23.3    23.3  23.3  25.0  23.3                               Ethanol  4.0     3.65    3.65  3.65  4.0   3.65                               HCl      0.01    0.74    0.74  0.74  0.01  0.74                               Chelant.sup.2                                                                          --      2.50    2.50  2.50  --    2.50                               Ammonium --      0.10    0.10  0.10  --    0.10                               Chloride                                                                      CaCl.sub.2                                                                             0.46    0.50    0.50  0.50  0.46  0.50                               Silicone 0.15    0.15    0.15  0.15  0.15  0.15                               Antifoam.sup.3                                                                Preservative.sup.4                                                                     0.0003  0.0003  0.0003                                                                              0.0003                                                                              0.0003                                                                              0.0003                             Perfume  --      --      1.35  1.35  1.20  1.00                               Soil Release                                                                           0.50    0.75    0.75  0.75  0.50  0.75                               Polymer.sup.5                                                                 Product of                                                                             0.50    0.25    --    0.25  --    --                                 Example 3.sup.6                                                               Product of                                                                             --      --      0.60  --    --    --                                 Example 11.sup.7                                                              Product of                                                                             --      --      --    --    1.0   --                                 Example 12.sup.8                                                              Product of                                                                             --      --      --    --    --    1.0                                Example 14.sup.9                                                              Water    69.38   68.06   66.36 66.71 67.68 66.31                              ______________________________________                                         .sup.1. Di(soft-tallowyloxyethyl) dimethyl ammonium chloride                  .sup.2. Diethylenetriamine Pentaacetic acid(3) DC2310, sold by DowCorning     .sup.3. DC2310, sold by DowCorning                                            .sup.4. Kathon CG, sold by Rohm & Has                                         .sup.5. Copolymer of propylene terephthalate and ethyleneoxide                .sup.6. 2,6dimethyl-7-octen-2-yl 3(4-nitrophenyl)-3-oxo-propionate.           .sup.7. 2,6dimethyl-7-octen-2-yl 3(nonanyl)-3-oxo-propionate.                 .sup.8. 3,7dimethyl-1,6-octadien-3-yl 3oxo-butyrate.                          .sup.9. 3,7dimethyl-1,6-octadien-3-yl (3(naphthyl)-3-oxo-propionate.     

Process

Example A is made in the following manner: A blend of 250g DEQA¹ and 40g ethanol are melted at about 70° C. A 25% aqueous solution of HCl inthe amount of 40 g is added to about 700 g of deionized water also at70° C. containing the antifoam. The DEQA/alcohol blend is added to thewater/HCl over a period of about five minutes with very vigorousagitation (IKA Paddle Mixer, model RW 20 DZM at 1500 rpm). A 25% aqueoussolution of CaCl₂ in the amount of 13.8 g is added to the dispersiondropwise over 1 minute, followed by milling with an IKA Ultra TurraxT-50 high shear mill for 5 minutes. The dispersion is then cooled toroom temperature by passing it through a plate and frame heat exchanger.Following cool-down, the soil release polymer is added into thedispersion in the form of a 40% solution and stirred for 10 minutes. Theproduct of Example 1 in the amount of 5.0 g is blended into thedispersion with moderate agitation. Finally, another 4.6 g of 25% CaCl₂is mixed into the dispersion and stirred for several hours.

Examples E is made in a like manner, excepting that the pro-perfumematerial is blended with the perfume component and the resulting mixtureis added to the cooled product.

Example B is made in the following manner: A blend of233 g DEQA¹ and36.5 g ethanol are melted at about 75° C. A 25% aqueous solution of HClin the amount of 0.3 g is added to about 680 g of deionized water alsoat 75° C. containing the antifoam. The DEQA/alcohol blend is added tothe water/HCl over a period of about two minutes with very vigorousagitation (IKA Padel Mixer, model RW 20 DZM at 1500 rpm). A 2.5% aqueoussolution of CaCl₂ in the amount of 2.5 g is added to the dispersiondropwise over 5 minutes, Meanwhile, 61 g of a 41% aqueous solution ofthe chelant is acidified by the addition of a 25% solution of HCl to ameasured pH of 3. A small amount, about 8g, of the acidified chelantsolution is stirred into the dispersion, followed by milling with an IKAUltra Turrax T-50 high shear mill for 5 minutes. The dispersion is thencooled to room temperature.

Following cool-down, the soil release polymer is added into thedispersion in the form of a 40% solution and stirred for 10 minutes. Theremaining acidified chelant solution is added over 3 minutes. Theproduct of Example 1 in the amount of 2.5g is added, followed by theaddition of ammonium chloride in the form of a 20% aqueous solution.Finally, the remaining CaCl₂ is added in the form of a 25% solution.

Examples C, D and F are made in a like manner, excepting that thepro-perfume material is blended with the perfume component and theresulting mixture is added to the cooled product.

Additional Formulation Examples

    ______________________________________                                                         G       H       I     J                                      Ingredient       Wt. %   Wt. %   Wt. % Wt. %                                  ______________________________________                                        DEQA.sup.1       19.2    19.2    18.2  19.2                                   Isopropyl alcohol                                                                              3.1     3.1     2.9   3.1                                    Tallow Alcohol Ethoxylate-25                                                                   --      --      1.20  --                                     Poly(glycerol monostearate)                                                                    --      --      2.40  --                                     HCl              0.02    0.02    0.08  0.02                                   CaCl.sub.2       0.12    0.12    0.18  0.12                                   Silicone Antifoam                                                                              0.02    0.02    0.02  0.02                                   Soil Release Polymer.sup.2                                                                     0.19    0.19    0.19  0.19                                   Poly(ethyleneglycol) 4000MW                                                                    0.60    0.60    0.60  0.60                                   Perfume          0.70    0.70    0.70  0.40                                   Product of Example 3.sup.3                                                                     0.58    --      --    --                                     Product of Example 12.sup.4                                                                    --      1.0     0.50  --                                     Product of Example 13.sup.5                                                                    --      --      0.50  --                                     Product of Example 7.sup.6                                                                     --      --      --    1.0                                    Water            75.47   75.05   72.53 75.35                                  ______________________________________                                         .sup.1. Di(hardtallowyloxyethyl) dimethyl ammonium chloride                   .sup.2. Copolymer of propylene terephthalate and ethyleneoxide                .sup.3. 3,7dimethyl-1,6-octadien-3-yl 3(naphthyl)-3-oxo-propionate.           .sup.4. 3,7dimethyl-1,6-octadien-3-yl 3(nonanyl)-3-oxo-propionate.            .sup.5. 2,6dimethyl-7-octen-2-yl 3(nonanyl)-3-oxo-propionate.                 .sup.6. 3,7dimethyl-1,6-octadien-3-yl 3(4-methoxyphenyl)-3-oxo-propionate

Additional Examples of Liquid Fabric Softener Compositions ContainingPro-perfumes

    ______________________________________                                        Formulation Example:                                                                        K          L       M                                            Ingredient    Wt. %      Wt. %   Wt. %                                        ______________________________________                                        DEQA.sup.1    10.35      10.35   10.35                                        Ethanol       1.40       1.40    1.40                                         HCl           0.0219     0.0219  0.0219                                       Blue Dye      0.0045     0.0045  0.0045                                       Silicone Antifoam.sup.2                                                                     0.015      0.015   0.015                                        Low Salt Kathon.sup.3                                                                       0.02       0.02    0.02                                         CaCl.sub.2    *          *       *                                            Product of Example 1.sup.4                                                                  0.25       0.50    --                                           Water         87.76      87.76   87.43                                        ______________________________________                                         *Added as needed to adjust viscosity                                          .sup.1. Di(hardtallowyloxyethyl) dimethyl ammonium chloride                   .sup.2. Silicone DC2310, sold by DowCorning                                   .sup.3. Kathon CG, sold by Rohm & Haas                                        .sup.4. 3,7dimethyl-1,6-octadien-3-yl 3(naphthyl)-3-oxo-proprionate.     

N. Experimental Procedure

A batch process is used. The procedure is divided in two parts: thepreparation of the base product (prepared in the lab. without perfumeand technology) and the addition of the perfume and the technology(ies).

Base product (to prepare a batch of 17 kg of base)

i. The main tank is loaded with the water needed (15.1 kg ) and isheated to 43° C. Start agitation at 800 rpm and mix blue dye . The mixerused is a Lightnin model LIU08.

ii. Add HCl (3.8 g) by hand (31% activity).

iii. Preheat DEQA (I)/ethanol at 75° C. (1760 g at 85% actives level )and inject into tank with water at a rate of 22 ml/min.

iv. Manually add low salt Kathon (3.4 g) and silicone antifoam (25.7 g).

v. Mix about 5 minutes

Finished product preparation (to prepare 0.250 kg of finished productcomposition)

vi. The product of Example 1 (0.625 g) is added to a 249 g aliquot ofthe above product by mixing with an IKA Ultra Turrax T-50 at 6000 rpmfor 15 minutes.

Examples L and M are made in a like manner, except that the pro-perfumematerial is added at the required amount.

What is claimed is:
 1. A rinse added fabric softening compositioncomprising:a) at least about 0.01% by weight, of a β-ketoester selectedfrom the group consisting of 3,7-dimethyl-1,6-octadien-3-yl3-(β-naphthyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl3-(4-methoxyphenyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl3-(4-nitrophenyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl3-(β-naphthyl)-3-oxo-propionate-3,7-dimethyl-1,6-octadien-3-yl3-(4-methoxyphenyl)-3-oxo-propionate,(α,α-4-trimethyl-3-cyclohexenyl)methyl 3-(β-naphthyl)-3-oxo-propionate,3,7-dimethyl-1,6-octadien-3-yl 3-(β-naphthyl)-3-oxo-propionate, cis3-hexen-1-yl 3-(β-naphthyl)-3-oxo-propionate, 9-decen-1-yl3-(β-naphthyl)-3-oxo-propionate 3,7-dimethyl-1,6-octadien-3-yl3-(nonanyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl3-(nonanyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-oxo-butyrate,3,7-dimethyl-1,6-octadien-3-yl 3-oxo-butyrate, 2,6-dimethyl-7-octen-2-yl3-(β-naphthyl)-3-oxo-2-methylpropionate 3,7-dimethyl-1,6-octadien-3-yl3-(β-naphthyl)-3-oxo-2,2-dimethylpropionate,3,7-dimethyl-1,6-octadien-3-yl 3-(β-naphthyl)-3-oxo-2-methylpropionate,3,7-dimethyl-2,6-octadienyl 3-(β-naphthyl)-3-oxo-propionate,3,7-dimethyl-2,6-octadienyl 3-heptyl-3-oxo-propionate, and mixturesthereof; and b) from about 85% to about 99.99% by weight, of ingredientsuseful for formulating fabric softening compositions wherein component(b) comprises one or more ingredients selected from the group consistingof cationic fabric softening agents, nonionic fabric softening agents,liquid carrier, concentration aid, soil release agent, perfume,preservatives, stabilizers, and mixtures thereof.
 2. A compositionaccording to claim 1 comprising from about 0.2% to about 1% by weight,of said β-ketoester.
 3. A composition according to claim 1 whereincomponent (b) comprises from about 1% to about 80%, by weight, of acationic fabric softening agent.
 4. A composition according to claim 1wherein component (b) comprises:i) from about 5% to about 50% by weight,of a cationic fabric softening agent; ii) at least about 50% of a liquidcarrier; and iii) optionally, from about 0 to about 15% by weight, ofconcentration aids.
 5. A composition according to claim 4 wherein saidcationic fabric softening agent is a quaternary ammonium compound havingthe formula: ##STR42## wherein Q has the formula: ##STR43## R is C₁ -C₆alkyl, C₁ -C₆ hydroxyalkyl, benzyl, and mixtures thereof; each R¹ isindependently linear or branched C₁₁ -C₂₂ alkyl, linear or branched C₁₁-C₂₂ alkenyl, and mixtures thereof; X is any softener compatible anion;m is 2 or 3; n is 1 to
 4. 6. A rinse added fabric softening compositioncomprising:a) at least about 0.01% by weight, of a β-ketoester havingthe formula: ##STR44## wherein R is selected from the group consistingof substituted or unsubstituted phenyl, substituted or unsubstitutedbenzyl, substituted or unsubstituted naphthyl, substituted orunsubstituted phenyl, substituted or unsubstituted nonanyl, substitutedor unsubstituted heptyl, and mixtures thereof; R¹ is an alkoxy unitderived from a fragrance raw material alcohol selected from the groupconsisting, of 4-(1-methylethyl)cyclohexane-methanol,2,4-dimethyl-3-cyclohexen-1-ylmethanol,(2,4-dimethylcyclohex-1-yl)methanol,(2,4,6-trimethyl-3-cyclohexen-1-yl)methanol, 2-phenylethanol,1-(4-isopropylcyclohexyl)-ethanol,2,2-dimethyl-3-(3-methylphenyl)propan-1-ol, 3-phenyl-2-propen-1-ol,2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol,3-methyl-5-phenylpentan-1-ol,3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol,2-methyl-4-phenylpentan-1-ol, cis-3-hexen-1-ol,3,7-dimethyl-6-octen-1-ol, 3,7-dimethyl-2,6-octadien-1-ol,7-methoxy-3,7-dimethyloctan-2-ol, 6,8-dimethylnonan-2-ol,cis-6-nonen-1-ol, 2,6-nonadien-1-ol, 4-methyl-3-decen-5-ol, benzylalcohol, 2-methoxy-4-(1-propenyl)phenol, 2-methoxy-4-(2-propenyl)phenol,3,7-dimethyl-octa-1,6-dien-3-ol, 2,6-dimethyl-octa-7-en-2-ol, andmixtures thereof,; R² and R³ are each independently selected from thegroup consisting of hydrogen, C₁ -C₂₀ substituted or unsubstitutedlinear alkyl, C₃ -C₂₀ substituted or unsubstituted branched alkyl, C₂-C₂₀ substituted or unsubstituted alkyleneoxy, C₃ -C₂₀ substituted orunsubstituted alkyleneoxyalkyl, C₇ -C₂₀ substituted or unsubstitutedalkylenearyl, C₆ -C₂₀ substituted or unsubstituted alkyleneoxyaryl, andmixtures thereof; and b) from about 5% to about 99.99% by weight, ofingredients useful for formulating fabric softening compositionscomprising:i) from about 5% to about 50% by weight, of a cationic fabricsoftening agent; ii) at least about 50% of a liquid carrier; and iii)optionally, from about 0 to about 15% by weight, of concentration aids.7. A composition according to claim 6 wherein the β-ketoesterpro-fragrance is selected from the group consisting of3,7-dimethyl-1,6-octadien-3-yl 3-(β-naphthyl)-3-oxo-propionate,2,6-dimethyl-7-octen-2-yl 3-(4-methoxyphenyl)-3-oxo-propionate,2,6-dimethyl-7-octen-2-yl 3-(4-nitrophenyl)-3-oxo-propionate,2,6-dimethyl-7-octen-2-yl 3-(,-naphthyl)-3-oxo-propionate,3,7-dimethyl-1,6-octadien-3-yl 3-(4-methoxyphenyl)-3-oxo-propionate,(α,α-4-trimethyl-3-cyclohexenyl)methyl 3-(β-naphthyl)-3-oxo-propionate,3,7-dimethyl-1,6-octadien-3-yl 3-(α-naphthyl)-3-oxo-propionate, cis3-hexen-1-yl 3-(β-naphthyl)-3-oxo-propionate, 9-decen-1-yl3-(β-naphthyl)-3-oxo-propionate, 3,7-dimethyl-1,6-octadien-3-yl3-(nonanyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl3-(nonanyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-oxo-butyrate,3,7-dimethyl-1,6-octadien-3-yl 3-oxo-butyrate, 2,6-dimethyl-7-octen-2-yl3-(β-naphthyl)-3-oxo-2-methylpropionate, 3,7-dimethyl-1,6-octadien-3-yl3-(β-naphthyl)-3-oxo-2-dimethylpropionate,3,7-dimethyl-1,6-octadien-3-yl 3-(β-naphthyl)-3-oxo-2-methylpropionate,3,7-dimethyl-2,6-octadienyl 3-(,-naphthyl)-3-oxo-propionate,3,7-dimethyl-2,6-octadienyl 3-heptyl-3-oxo-propionate, and mixturesthereof; and wherein the fabric softening agent is a quaternary ammoniumcompound having the formula: ##STR45## wherein Q has the formula:##STR46## R is C₁ -C₆ alkyl, C₁ -C₆ hydroxyalkyl, benzyl, and mixturesthereof; each R¹ is independently linear or branched C₁₁ -C₂₂ alkyl,linear or branched C₁₁ -C₂₂ alkenyl, and mixtures thereof; X is anysoftener compatible anion; m is 2 or 3; n is 1 to
 4. 8. A compositionaccording to claim 1 comprising from about 0.01% to about 15% by weight,of said β-ketoester.
 9. A composition according to claim 8 comprisingfrom about 0.1% to about 10% by weight, of said β-ketoester.
 10. Acomposition according to claim 1 wherein said fabric softening active isselected from the group consisting of:i) an quaternary ammonium compoundhaving the formula: ##STR47## ii) a quaternary ammonium compound havingthe formula: ##STR48## iii) and mixtures thereof; wherein each R isindependently C₁ -C₆ alkyl, C₁ -C₆ hydroxyalkyl, and mixtures thereof;R¹ is C₁₁ -C₂₂ linear alkyl, C₁₁ -C₂₂ branched alkyl, C₁₁ -C₂₂ linearalkenyl, C₁₁ -C₂₂ branched alkenyl, and mixtures thereof; Q is acarbonyl moiety independently selected from units having the formula:##STR49## wherein R² is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl, andmixtures thereof; R³ is hydrogen, C₁ -C₄ alkyl, and mixtures thereof; Xis selected from the group consisting of chloride, bromidesmethylsulfate, ethylsulfate, sulfate, nitrate, and mixtures thereof; theindex m has the value from 1 to 4, the index n has the value from 1 to4.
 11. A composition according to claim 10 wherein Q has the formula:##STR50##
 12. A composition according to claim 11 wherein the moiety--O₂ CR¹ comprises an acyl unit, said acyl unit derived from a source oftriglyceride selected from the group consisting of tallow, partiallyhydrogenated tallow, lard, partially hydrogenated lard, vegetable oilsand/or partially hydrogenated vegetable oils, canola oil, safflower oil,peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice branoil, and mixtures thereof.
 13. A composition according to claim 10wherein R is methyl, hydroxyalkyl, and mixtures thereof.
 14. Acomposition according to claim 13 wherein n is equal to 2.